Alkylated urea and triaminotriazine compounds and phase change inks containing same

ABSTRACT

Disclosed are compounds of the formulae  
                 

                 
 
     wherein Z is a group of the formula —OR 1 , a group of the formula —SR 1 , or a group of the formula —NR 1 R 2 , Y is a group of the formula —OR 3 , a group of the formula —SR 3 , or a group of the formula —NR 3 R 4 , n is an integer representing the number of repeat —(CH 2 )— or —(CH 2 CH 2 O)— units, wherein, provided that at least one of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6  is a hydrogen atom, provided that at least one of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6  is other than a hydrogen atom, and provided that at least one Z or Y within the compound is a group of the formula —NR 1 R 2  or a group of the formula —NR 3 R 4 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7  each, independently of the others, is (i) a hydrogen atom, (ii) an alkyl group, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylaryl group, and wherein R 7  can also be (vi) an alkoxy group, (vii) an aryloxy group, (viii) an arylalkyloxy group, (ix) an alkylaryloxy group, (x) a polyalkyleneoxy group, (xi) a polyaryleneoxy group, (xii) a polyarylalkyleneoxy group, (xiii) a polyalkylaryleneoxy group, (xiv) a silyl group, (xv) a siloxane group, (xvi) a polysilylene group, (xvii) a polysiloxane group, or (xviii) a group of the formula  
                 
 
     wherein r is an integer representing a number of repeat —CH 2 — groups, wherein s is an integer representing a number of repeating —CH 2 — groups, and wherein X is (a) a direct bond, (b) an oxygen atom, (c) a sulfur atom, (d) a group of the formula —NR 40 — wherein R 40  is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, or (e) a group of the formula —CR 50 R 60 — wherein R 50  and R 60  each, independently of the other, is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, and wherein R 6  can also be  
                 
 
     Also disclosed are phase change ink compositions comprising a colorant and a phase change ink carrier comprising a material of this formula.

CROSS-REFERENCE IS MADE TO THE FOLLOWING APPLICATIONS

[0001] Copending Application U.S. Ser. No. 09/949,315, filed Sep. 7,2001, entitled “Aqueous Ink Compositions,” with the named inventorsThomas W. Smith, David J. Luca, and Kathleen M. McGrane, the disclosureof which is totally incorporated herein by reference, discloses anaqueous ink composition comprising an aqueous liquid vehicle, acolorant, and an additive wherein, when the ink has been applied to arecording substrate in an image pattern and a substantial amount of theaqueous liquid vehicle has either evaporated from the ink image,hydrogen bonds of sufficient strength exist between the additivemolecules so that the additive forms hydrogen-bonded oligomers orpolymers.

[0002] Copending Application U.S. Ser. No. 09/948,958, filed Sep. 7,2001, entitled “Phase Change Ink Compositions,” with the named inventorsH. Bruce Goodbrand, Thomas W. Smith, Dina Popovic, Daniel A. Foucher,and Kathleen M. McGrane, the disclosure of which is totally incorporatedherein by reference, discloses a phase change ink composition comprisinga colorant and an ink vehicle, the ink being a solid at temperaturesless than about 50° C. and exhibiting a viscosity of no more than about20 centipoise at a jetting temperature of no more than about 160° C.,wherein at a first temperature hydrogen bonds of sufficient strengthexist between the ink vehicle molecules so that the ink vehicle formshydrogen-bonded dimers, oligomers, or polymers, and wherein at a secondtemperature which is higher than the first temperature the hydrogenbonds between the ink vehicle molecules are sufficiently broken thatfewer hydrogen-bonded dimers, oligomers, or polymers are present in theink at the second temperature than are present in the ink at the firsttemperature, so that the viscosity of the ink at the second temperatureis lower than the viscosity of the ink at the first temperature.

[0003] Copending Application U.S. Serial No. (not yet assigned; AttorneyDocket No. D/A 1722), filed concurrently herewith, entitled “AlkylatedTetrakis(triaminotriazine) Compounds and Phase Change Inks ContainingSame,” with the named inventors Danielle C. Boils-Boissier, Marcel P.Breton, Jule W. Thomas, Jr., Donald R. Titterington, Jeffery H. Banning,H. Bruce Goodbrand, James D. Wuest, Marie-Ève Perron, Francis Monchamp,and Hugues Duval, the disclosure of which is totally incorporated hereinby reference, discloses compounds of the formula

[0004] wherein, provided that at least one of R₁, R₂, R₃, R₄, R₅, and R₆is a hydrogen atom, and provided that at least one of R₁, R₂, R₃, R₄,R₅, and R₆ is not a hydrogen atom, R₁, R₂, R₃, R₄, R₅, and R₆ each,independently of the others, is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup. Also disclosed are phase change ink compositions comprising acolorant and a phase change ink carrier comprising a material of thisformula.

[0005] Copending Application U.S. Serial No. (not yet assigned; AttorneyDocket No. D/A2176), filed concurrently herewith, entitled““Guanidinopyrimidinone Compounds and Phase Change Inks ContainingSame,” with the named inventors Danielle C. Boils-Boissier, Marcel P.Breton, Jule W. Thomas, Jr., Donald R. Titterington, Jeffery H. Banning,H. Bruce Goodbrand, James D. Wuest, Marie-Eve Perron, and Hugues Duval,the disclosure of which is totally incorporated herein by reference,discloses compounds of the formulae

[0006] wherein, provided that at least one of R₁, R₂, and R₃ is not ahydrogen atom, R₁, R₂, and R₃ each, independently of the other, is (i) ahydrogen atom, (ii) an alkyl group, (iii) an aryl group, (iv) anarylalkyl group, or (v) an alkylaryl group, and wherein R₁ and R₂ canalso be (vi) an alkoxy group, (vii) an aryloxy group, (viii) anarylalkyloxy group, (ix) an alkylaryloxy group, (x) a polyalkyleneoxygroup, (xi) a polyaryleneoxy group, (xii) a polyarylalkyleneoxy group,(xiii) a polyalkylaryleneoxy group, (xiv) a silyl group, (xv) a siloxanegroup, (xvi) a polysilylene group, (xvii) a polysiloxane group, or(xviii) a group of the formula

[0007] wherein r is an integer representing a number of repeat —CH₂—groups, wherein s is an integer representing a number of repeating —CH₂—groups, and wherein X is (a) a direct bond, (b) an oxygen atom, (c) asulfur atom, (d) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogenatom, an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (e) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and R₁₀ and R₁₁ each,independently of the other, is (i) an alkylene group, (ii) an arylenegroup, (iii) an arylalkylene group, or (iv) an alkylarylene group, andwherein R₁₀ can also be (v) a polyalkyleneoxy group, (vi) apolyaryleneoxy group, (vii) a polyarylalkyleneoxy group, (viii) apolyalkylaryleneoxy group, (ix) a silylene group, (x) a siloxane group,(xi) a polysilylene group, or (xii) a polysiloxane group. Also disclosedare phase change ink compositions comprising a colorant and a phasechange ink carrier comprising a material of this formula.

[0008] Copending application U.S. Ser. No. ______ (not yet assigned;Attorney Docket No. D/A2403), filed concurrently herewith, entitled“Phase Change Inks Containing Gelator Additives,” with the namedinventors Marcel P. Breton, Danielle C. Boils-Boissier, Donald R.Titterington, Jule W. Thomas, Jr., Jeffery H. Banning, Christy Bedford,and James D. Wuest, the disclosure of which is totally incorporatedherein by reference, discloses a phase change ink composition comprisingan ink vehicle, a colorant, and a nonpolymeric organic gelator selectedfrom the group consisting of anthracene-based compounds, steroidcompounds, partially fluorinated high molecular weight alkanes, highmolecular weight alkanes with exactly one hetero atom, chiral tartratecompounds, chiral butenolide-based compounds, bis-urea compounds,guanines, barbiturates, oxamide compounds, ureidopyrimidone compounds,and mixtures thereof, said organic gelator being present in the ink inan amount of no more than about 20 percent by weight of the ink, saidink having a melting point at or below which the ink is a solid, saidink having a gel point at or above which the ink is a liquid, and saidink exhibiting a gel state between the melting point and the gel point,said ink exhibiting reversible transitions between the solid state andthe gel state upon heating and cooling, said ink exhibiting reversibletransitions between the gel state and the liquid state upon heating andcooling, said melting point being greater than about 35° C., said gelpoint being greater than said melting point. Also disclosed are imagingprocesses employing phase change inks containing gelator additives.

BACKGROUND OF THE INVENTION

[0009] The present invention is directed to alkylated urea andtriaminotriazine compounds and to phase change (hot melt) inkcompositions. More specifically, the present invention is directed tocompositions of matter and to phase change ink compositions suitable foruse in ink jet printing processes that contain these compositions. Oneembodiment of the present invention is directed to compounds of theformulae

[0010] wherein Z is a group of the formula —OR₁, a group of the formula—SR₁, or a group of the formula —NR₁R₂, Y is a group of the formula—OR₃, a group of the formula —SR₃, or a group of the formula —NR₃R₄, nis an integer representing the number of repeat —(CH₂)— or —(CH₂CH₂O)—units, wherein, provided that at least one of R₁, R₂, R₃, R₄, R₅, and R₆is a hydrogen atom, provided that at least one of R₁, R₂, R₃, R₄, R₅,and R₆ is other than a hydrogen atom, and provided that at least one Zor Y within the compound is a group of the formula —NR₁R₂ or a group ofthe formula —NR₃R₄, R₁, R₂, R₃, R₄, R₅, R₆, and R₇ each, independentlyof the others, is (i) a hydrogen atom, (ii) an alkyl group, (iii) anaryl group, (iv) an arylalkyl group, or (v) an alkylaryl group, andwherein R₇ can also be (vi) an alkoxy group, (vii) an aryloxy group,(viii) an arylalkyloxy group, (ix) an alkylaryloxy group, (x) apolyalkyleneoxy group, (xi) a polyaryleneoxy group, (xii) apolyarylalkyleneoxy group, (xiii) a polyalkylaryleneoxy group, (xiv) asilyl group, (xv) a siloxane group, (xvi) a polysilylene group, (xvii) apolysiloxane group, or (xviii) a group of the formula

[0011] wherein r is an integer representing a number of repeat —CH₂—groups, wherein s is an integer representing a number of repeating —CH₂—groups, and wherein X is (a) a direct bond, (b) an oxygen atom, (c) asulfur atom, (d) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogenatom, an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (e) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and wherein R₆ canalso be

[0012] Another embodiment of the present invention is directed to aphase change ink composition comprising a colorant and a phase changeink carrier comprising a material of this formula.

[0013] In general, phase change inks (sometimes referred to as “hot meltinks”) are in the solid phase at ambient temperature, but exist in theliquid phase at the elevated operating temperature of an ink jetprinting device. At the jet operating temperature, droplets of liquidink are ejected from the printing device and, when the ink dropletscontact the surface of the recording substrate, either directly or viaan intermediate heated transfer belt or drum, they quickly solidify toform a predetermined pattern of solidified ink drops. Phase change inkshave also been used in other printing technologies, such as gravureprinting, as disclosed in, for example, U.S. Pat. No. 5,496,879 andGerman Patent Publications DE 4205636AL and DE 4205713AL, thedisclosures of each of which are totally incorporated herein byreference.

[0014] Phase change inks for color printing typically comprise a phasechange ink carrier composition which is combined with a phase change inkcompatible colorant. In a specific embodiment, a series of colored phasechange inks can be formed by combining ink carrier compositions withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks can comprise four component dyes, namely,cyan, magenta, yellow and black, although the inks are not limited tothese four colors. These subtractive primary colored inks can be formedby using a single dye or a mixture of dyes. For example, magenta can beobtained by using a mixture of Solvent Red Dyes or a composite black canbe obtained by mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat.No. 4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each ofwhich are totally incorporated herein by reference, teach that thesubtractive primary colorants employed can comprise dyes from theclasses of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acidand Direct Dyes, and Basic Dyes. The colorants can also includepigments, as disclosed in, for example, U.S. Pat. No. 5,221,335, thedisclosure of which is totally incorporated herein by reference. U.S.Pat. No. 5,621,022, the disclosure of which is totally incorporatedherein by reference, discloses the use of a specific class of polymericdyes in phase change ink compositions.

[0015] Phase change inks have also been used for applications such aspostal marking and industrial marking and labelling.

[0016] Phase change inks are desirable for ink jet printers because theyremain in a solid phase at room temperature during shipping, long termstorage, and the like. In addition, the problems associated with nozzleclogging as a result of ink evaporation with liquid ink jet inks arelargely eliminated, thereby improving the reliability of the ink jetprinting. Further, in phase change ink jet printers wherein the inkdroplets are applied directly onto the final recording substrate (forexample, paper, transparency material, and the like), the dropletssolidify immediately upon contact with the substrate, so that migrationof ink along the printing medium is prevented and dot quality isimproved.

[0017] Compositions suitable for use as phase change ink carriercompositions are known. Some representative examples of referencesdisclosing such materials include U.S. Pat. No. 3,653,932, U.S. Pat. No.4,390,369, U.S. Pat. No. 4,484,948, U.S. Pat. No. 4,684,956, U.S. Pat.No. 4,851,045, U.S. Pat. No. 4,889,560, U.S. Pat. No. 5,006,170, U.S.Pat. No. 5,151,120, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,496,879,European Patent Publication 0187352, European Patent Publication0206286, German Patent Publication DE 4205636AL, German PatentPublication DE 4205713AL, and PCT Patent Application WO 94/04619, thedisclosures of each of which are totally incorporated herein byreference. Suitable carrier materials can include paraffins,microcrystalline waxes, polyethylene waxes, ester waxes, fatty acids andother waxy materials, fatty amide containing materials, sulfonamidematerials, resinous materials made from different natural sources (talloil rosins and rosin esters, for example), and many synthetic resins,oligomers, polymers, and copolymers.

[0018] U.S. Pat. No. 5,006,170 (Schwarz et al.) and U.S. Pat. No.5,122,187 (Schwarz et al.), the disclosures of each of which are totallyincorporated herein by reference, disclose hot melt ink compositionssuitable for ink jet printing which comprise a colorant, a binder, and apropellant selected from the group consisting of hydrazine; cyclicamines; ureas; carboxylic acids; sulfonic acids; aldehydes; ketones;hydrocarbons; esters; phenols; amides; imides; halocarbons; urethanes;ethers; sulfones; sulfamides; sulfonamides; phosphites; phosphonates;phosphates; alkyl sulfines; alkyl acetates; and sulfur dioxide. Alsodisclosed are hot melt ink compositions suitable for ink jet printingwhich comprise a colorant, a propellant, and a binder selected from thegroup consisting of rosin esters; polyamides; dimer acid amides; fattyacid amides; epoxy resins; fluid paraffin waxes; fluid microcrystallinewaxes; Fischer-Tropsch waxes; polyvinyl alcohol resins; polyols;cellulose esters; cellulose ethers; polyvinyl pyridine resins; fattyacids; fatty acid esters; poly sulfonamides; benzoate esters; long chainalcohols; phthalate plasticizers; citrate plasticizers; maleateplasticizers; sulfones; polyvinyl pyrrolidinone copolymers; polyvinylpyrrolidone/polyvinyl acetate copolymers; novalac resins; naturalproduct waxes; mixtures of linear primary alcohols and linear long chainamides; and mixtures of linear primary alcohols and fatty acid amides.In one embodiment, the binder comprises a liquid crystalline material.

[0019] U.S. Pat. No. 5,021,802 (Allred), the disclosure of which istotally incorporated herein by reference, discloses impulse ink orbubble jet inks which comprise 90 to 99.9 percent by weight of aqueoussol-gel medium and 0.1 to 10 percent by weight colorant. The inks arethermally reversible sol-gels which are gels at ambient temperatures andsols at temperatures between about 400 to 100° C.

[0020] U.S. Pat. No. 5,180,425 (Matrick et al.), the disclosure of whichis totally incorporated herein by reference, discloses an ink for inkjet printers which comprises an aqueous carrier medium, pigmentdispersion or dye, and a polyol/alkylene oxide condensate cosolventwhich eliminates film formation on thermal ink jet resistor surfacesthereby eliminating non-uniformity in optical density. The cosolventpresent at least 5 percent has a solubility in water of at least 4.5parts in 100 parts of water at 25° C. and a general formula:

[0021] wherein X=—H or —CH₃; R=—H, —CH₃, —C₂H₅, —C₃H₇, —C₄H₉, or—CH₂O(CH₂CH₂O)_(e)H; b=0 or 1, a+d+f(c+e)=2 to 100; and f=1 to 6, thecosolvent being present in the amount of at least 4.5 percent based onthe total weight of the ink jet ink composition. These inks exhibitfreedom from thermal resistor film formation, have excellent decapperformance, are storage stable and give images having excellent printquality.

[0022] U.S. Pat. No. 5,531,817 (Shields et al.), the disclosure of whichis totally incorporated herein by reference, discloses the control ofcolor bleed (the invasion of one color into another on the surface ofthe print medium) using ink-jet inks by employing either high molecularweight polymers that exhibit a reversible gelling nature with heat orcertain amine oxide surfactants that undergo sol-gel transitions. Theinks of the invention further include a vehicle and a dye. The vehicletypically comprises a low viscosity, high boiling point solvent andwater. Certain high molecular weight polymers, under the correctsolution conditions, can form gels which can be subsequently melted byheating of the gel. When the melted gel is cooled, it will then reforminto a gel. The viscosity of an ink employing such a gel can be reducedto a viscosity low enough to permit jetting from the print cartridge.After leaving the print cartridge, the melted gel will again reform intoa highly viscous gel to immobilize the droplet of ink and prevent itsmigration on the media. Therefore, two drops of different colors, whenprinted next to one another will thus be inhibited from migrating orbleeding into one another.

[0023] U.S. Pat. No. 5,476,540 (Shields et al.), the disclosure of whichis totally incorporated herein by reference, discloses a method forcontrolling color bleed between adjacent multi-color ink regions on aprint medium. Color bleed involves the migration of color agents betweenadjacent zones in a multicolored printed image on a print medium. Afirst composition containing a gel-forming species and a color agent isbrought into contact on a region of the print medium with a secondcomposition having a color agent and a gel-initiating species orchemical conditions which bring about gelation. In alternativeembodiments, the print medium may be pretreated with either agel-initiating species or a gel-forming species (with no colorant),followed by treatment with a gel-forming species or gel-initiatingspecies (with colorant), respectively. The formation of the gel upon theprint medium impedes the movement of the color agent or agents and thusreduces the color bleed between adjacent zones.

[0024] U.S. Pat. No. 5,389,958 (Bui et al.), the disclosure of which istotally incorporated herein by reference, discloses a method andapparatus whereby an intermediate transfer surface of a layer ofsacrificial liquid is applied to a supporting surface and a phase changeink is deposited on the liquid layer. The inked image is then contacttransferred to a final receiving substrate.

[0025] U.S. Pat. No. 5,554,212 (Bui et al.), the disclosure of which istotally incorporated herein by reference, discloses an aqueous phasechange ink containing a water dispersible sulfonated polyester glossagent and a selected concentration of hyperthermogelling component thatcauses the ink to gel when its temperature is increased to itsthermo-inversion point or when the concentration of thehyperthermogelling component is increased by evaporation, or substrateabsorption, of water from the ink. The ink may be jetted directly onto aheated and/or absorptive substrate or jetted onto a cooler and/orhydrophobic surface before being transferred to the substrate. Thethermo-inversion point is preferably about ambient temperature, and thepreferred hyperthermogelling component is a nonionic surfactant, such asan ethylene oxide propylene oxide block copolymer surfactant.

[0026] U.S. Pat. No. 5,462,591 (Karandikar et al.), the disclosure ofwhich is totally incorporated herein by reference, discloses an aqueousphase change ink that contains a selected concentration ofhyperthermogelling component that causes the ink to gel when itstemperature is increased to its thermo-inversion point or when theconcentration of the hyperthermogelling component is increased byevaporation, or substrate absorption, of water from the ink. The ink maybe jetted directly onto a heated and/or absorptive substrate or jettedonto a cooler and/or hydrophobic surface before being transferred to thesubstrate. The thermo-inversion point is preferably about ambienttemperature, and the preferred hyperthermogelling component is anonionic surfactant, such as an ethylene oxide propylene oxide blockcopolymer surfactant.

[0027] U.S. Pat. No. 5,099,256 (Anderson), the disclosure of which istotally incorporated herein by reference, discloses an ink jet printerhaving a rotatable intermediate drum having a thermally conductivesurface on which the ink droplets are printed from the printhead. Thedrum surface material is a suitable film forming silicone polymer havinga high surface energy and surface roughness to prevent movement of thedroplets after impact thereon. The printhead is located relative to theintermediate drum surface so that the ink droplets impact the drumsurface with a large contact angle and the ink droplet image istransferred at a second location spaced from the printhead to minimizecontaminating particles from the recording medium from reaching theprinthead nozzles. The intermediate drum surface is heated to dehydratethe ink droplets prior to transfer from the intermediate drum to therecording medium. The silicone polymer coating enables substantiallycomplete transfer of the dehydrated droplets to the recording medium, sothat subsequent removal of the residual ink from the drum by a cleaningsystem is eliminated.

[0028] U.S. Pat. No. 4,538,156 (Durkee et al.), the disclosure of whichis totally incorporated herein by reference, discloses an ink jetprinter utilizing a smooth surfaced transfer drum as an illustrativeembodiment of the invention. The transfer drum and the print headassembly are mounted between a pair of side plates. A print headassembly, which comprises a number of ink jet nozzles, is also mountedbetween the side plates. The print head assembly is spaced apart fromthe drum and the nozzles thereof are spaced at equal distances along aline which is parallel to the axis of the drum. The print head assemblyis movable in fine steps from left to right so that on successiverotations of the drum each nozzle is directed to a new track of asuccession of tracks. After all tracks of the transfer drum have beenserved by a nozzle assembly, a printing medium, e.g., paper is broughtin rolling contact with the drum to transfer the indicia on the drum tothe printing medium while the print head assembly is returned to itsstarting position; and thereafter, if required, the drum is wiped cleanin preparation for receiving the next page of information.

[0029] U.S. Pat. No. 5,761,597 (Smith et al.), the disclosure of whichis totally incorporated herein by reference, discloses an improvedfusing apparatus for fixing or fusing images on print media wherein arelatively small pressure applying surface, such as the surface of arotatable pressure wheel, is lubricated with a lubricating medium suchas silicone oil, and engages the printed image to apply pressure andfuse the image to the image receiving substrate. The fusing apparatus ismounted for reciprocal back and forth movement across the printed imageon the image receiving substrate or medium to fuse the image into thesubstrate and flatten or smooth the upper exposed surface of the inkimage. The pressure wheel is passed in multiple overlapping passes overthe printed image to uniformly fuse the image into the media.

[0030] U.S. Pat. No. 5,195,430 (Rise), the disclosure of which istotally incorporated herein by reference, discloses a fixing anddeveloping apparatus in which sheet material to be treated is passedthrough a high pressure nip defined by a pair of rollers. At least oneof the rollers may have a composite construction. The composite rollerincludes an elongated tubular shell with a pressure applying externalsurface, an elongated core positioned within the tubular shell, and anelastomeric material disposed between the core and shell to support theshell on the core. The core may be of a number of configurations and mayincrease in transverse cross-sectional dimension from the respectiveends of the core toward the center of the core. The core may tapercontinuously or in discrete steps from its center toward its first andsecond ends. In addition, the core may have a longitudinal cross-sectionwith a crown in the shape of a beam deflection curve for a simplysupported, uniformly constant cross-section beam. The shell may besimilarly configured along its interior surface. Also, the elastomer maybe compressed at the center of the roller relative to the ends of theroller to preload its center portion.

[0031] U.S. Pat. No. 4,889,761 (Titterington et al.), the disclosure ofwhich is totally incorporated herein by reference, discloses a methodfor producing a light-transmissive phase change ink printed substratewhich comprises providing a substrate, and then printing on at least onesurface of the substrate a predetermined pattern of a light-transmissivephase change ink which initially transmits light in a non-rectilinearpath. The pattern of solidified phase change ink is then reoriented toform an ink layer of substantially uniform thickness. This ink layerwill, in turn, produce an image which then will transmit light in asubstantially rectilinear path. In one aspect of the invention, thesubstrate is light transmissive, and the reoriented printed substrateexhibits a high degree of lightness and chroma, and transmits light in asubstantially rectilinear path. In this way, the reoriented printedsubstrate can be used in a projection device to project an imagecontaining clear, saturated colors.

[0032] U.S. Pat. No. 4,745,420 (Gerstenmaier), the disclosure of whichis totally incorporated herein by reference, discloses a method ofejecting droplets of phase change or hot melt ink jet ink upon a targetsuch as paper which includes a step of applying pressure to the dropletsafter they have cooled upon the paper in order to increase theircoverage and, thus, minimize the volume of ink required to produce ahigh quality print with a high degree of resolution. Including a meansfor applying pressure to the cooled droplets, a suitable apparatusincreases the area of the target covered by a particular droplet afterspreading by at least five percent and preferably by twenty percent.

[0033] U.S. Pat. No. 6,320,018 (Sijbesma et al.), the disclosure ofwhich is totally incorporated herein by reference, discloses a polymercomprising monomeric units linked via four H-bridges and bound withinsaid polymer via a different bond. The bond via the H-bridges is muchstronger than with known supramolecular polymers.

[0034] U.S. Pat. No. 5,892,116 (Weiss et al.) and PCT Patent PublicationWO 97/24364 (Weiss et al.), the disclosures of each of which are totallyincorporated herein by reference, disclose gelators that gel a varietyof nonpolar and polar liquids. Moreover, gelation of various monomerswith subsequent polymerization of the gelled monomers forms organiczeolites and membrane materials. An ionic gelator includes salts ofcompounds of formula (I)

[R¹R²R³X—R⁴]^(±)Y^(±)  I

[0035] where R¹, R², and R³ are the same or different hydrogen ororganic groups including alkyl groups, alkenyl groups, alkynyl groups,aryl groups, arylalkyl groups, alkoxy groups, aryloxy groups; X is aGroup IIIA or Group VA element; R⁴ is a steroidal group, an alkyl group,an alkenyl group, an alkynyl group, an aryl group, an arylalkyl group,an alkoxy group, or an aryloxy group; and Y is a Group IA or Group VIIAelement or one-half of a Group IIA or VIA element, that is, a divalentcounterion. The gelling agent composition may include a single isomer ormixtures of isomers of the formula (I). A non-ionic gelator alsoincludes compounds of the formula (II):

R¹R²R³X  II

[0036] where R¹, R², R³, and X are defined as above.

[0037] Also of interest with respect to the present invention are thefollowing references: “Reversible Polymers Formed fromSelf-Complementary Monomers Using Quadruple Hydrogen Bonding,” R. P.Sijbesma et al., Science, Vol. 278, p. 1601 (1997); “SupramolecularPolymers,” R. Dagani, Chemical and Engineering News, p. 4 (December1997); “Supramolecular Polymers from Linear Telechelic Siloxanes withQuadruple-Hydrogen-Bonded Units,” J. H. K. Hirschberg et al.,Macromolecules, Vol. 32, p. 2696 (1999); “Design and Synthesis of‘Smart’ Supramolecular Liquid Crystalline Polymers via Hydrogen-BondAssociations,” A. C. Griffin et al., PMSE Proceedings, Vol. 72, p. 172(1995); “The Design of Organic Gelators: Solution and Solid StateProperties of a Family of Bis-Ureas,” Andrew J. Carr et al., TetrahedronLetters, Vol. 39, p. 7447 (1998); “Hydrogen-Bonded SupramolecularPolymer Networks,” Ronald F. M. Lange et al., Journal of PolymerScience, Part A: Polymer Chemistry, Vol. 37, p. 3657 (1999); “CombiningSelf-Assembly and Self-Association—Towards Columnar SupramolecularStructures in Solution and in Liquid-Crystalline Mesophase,” Arno Kraftet al., Polym. Mater. Sci. Eng., Vol. 80, p. 18 (1999); “FacileSynthesis of β-Keto Esters from Methyl Acetoacetate and Acid Chloride:The Barium Oxide/Methanol System,” Y. Yuasa et al., Organic ProcessResearch and Development, Vol. 2, p. 412 (1998); “Self-ComplementaryHydrogen Bonding of 1,1′-Bicyclohexylidene-4,4′-dione Dioxime. Formationof a Non-Covalent Polymer,” F. Hoogesteger et al., Tetrahedron, Vol. 52,No. 5, p. 1773 (1996); “Molecular Tectonics. Three-Dimensional OrganicNetworks with Zeolite Properties,” X. Wang et al., J. Am. Chem. Soc.,Vol. 116, p. 12119 (1994); “Helical Self-Assembled Polymers fromCooperative Stacking of Hydrogen-Bonded Pairs,” J. H. K. Ky Hirschberget al., Nature, Vol. 407, p. 167 (2000); “New Supramolecular Arraysbased on Interactions between Carboxylate and Urea Groups: Solid-Stateand Solution Behavior,” Abdullah Zafar et al., New J. Chem., 1998,137-141; “The Unusual Molecular Organization of2,3-Bis(n-hexyloxy)-anthracene in the Crystal. A Hint to the Origin ofthe Gelifying Properties of 2,3-Bis(n-alkyloxy)anthracenes?”, J-L. Pozzoet al., J. Chem. Soc., Perkin Trans., 2, 824-826 (2001); “The Quest forthe Simplest Possible Organogelators and Some Properties of theirOrganogels,” D. Abdallah et al., J. Braz. Chem. Soc., Vol. 11, No. 3,209-218 (2000); “Organogel Electrolytes Based on a Low Molecular WeightGelator: 2,3-Bis(n-decyloxy)anthracene,” F. Placin et al., Chem. Mater.13, 117-121 (2001); “Novel Vesicular Aggregates of Crown-AppendedCholesterol Derivatives Which Act as Gelators of Organic Solvents and asTemplates for Silica Transcription,” J. Jung et al., J. Am. Chem. Soc.,Vol. 122, No. 36, 8648-8653 (2000); “n-Alkanes Gel n-Alkanes (and ManyOther Organic Liquids),” D. Abdallah et al., Langmuir, 16, 352-355(2000); “Low Molecular Mass Gelators of Organic Liquids and theProperties of their Gels,” P. Terech et al., Chem. Rev., 97, 3133-3159(1997); “Organogels and Low Molecular Mass Organic Gelators,” D.Abdallah et al., Adv. Mater., 12, No. 17, 1237 (2000); “Making it AllStick Together: the Gelation of Organic Liquids by Small OrganicMolecules,” F. Schoonbeek, Doctoral Thesis, U. of Groningen,Netherlands, April 2001; Twieg et al., Macromolecules, Vol. 18, p. 1361(1985); “Synthesis and Reactions of Polyhydric Alcohols I. Synthesis andReactions of p-Toluenesulfonates of Polyhydric Alcohols,” ZhurnalObshchei Khimii, Vol. 35, No. 5, p. 804-807 (1965); “The Chemotherapy ofSchistosomiasis. Part I. Derivatives and Analogs ofαω-Di-(p-aminophenoxy)alkanes,” J. Ashley et al., J. Chem. Soc. 1958,3293; “Remarkably Simple Small Organogelators: Di-n-alkoxy-benzeneDerivatives,” G. Clavier et al., Tetrahedron Letters, 40, 9021-9024(1999); “Rational Design of Low Molecular Mass Organogelators: Toward aLibrary of Functional N-Acyl-1-ω-Amino Acid Derivatives,” G.Mieden-Gundert et al., Angew. Chem. Int. Ed., 40, No. 17, 3164-3166(2001); U.S. Pat. No. 2,703,808 (Buchman); “Rational Design of NewAcid-Sensitive Organogelators,” J-L. Pozzo et al., J. Mater. Chem., Vol.8, pp. 2575-2577 (1998); J. T. Thurston et al., J. Am. Chem. Soc., Vol.73, pp. 2981-3008 (1951); J. Am. Chem. Soc., Vol. 96, pp. 1082-1087(1974); J-L. Pozzo et al., Tetrahedron, Vol. 53, No. 18, pp. 6377-6390(1997); J-L. Pozzo et al., Mol. Cryst. Liq. Cryst., Vol. 344, pp.101-106 (2000); Y. C. Lin, R. G. Weiss,

[0038] Macromolecules, Vol. 20, p. 414 (1987); Weiss et al., U.S. Pat.No. 4,790,961; Murata et al, J. Am. Chem. Soc., Vol. 116, No 15, pp.6664-6676 (1994); A. Ikeda et al., Rep. Asahi Glass Found. Ind.Technol., Vol. 61, p. 115, (1992); Rabolt et al., Macromolecules, Vol.17, p. 2786 (1984); D. J. Abdallah et al., Chem. Mater., Vol. 11, p.2907 (1999); Ralston et al., J. Org. Chem., Vol. 9, p. 259 (1944); L. Luet al., Chem. Commun., 1996, p. 2029; J. Prakt. Chem., Vol. 327 (3), pp.383-98 (1985); B. L. Feringa et al., J. Org. Chem., Vol. 53, p. 1125(1988); J. C. DeJong et al., Tetrahedron Lett., Vol. 30, p. 7239 (1989);J. C. DeJong, Ph.D. thesis, University of Groningen, The Netherlands,1991; F. A. Neugebauer et al., Chem. Ber., 1976, 109, 2389; U. Zehavi etal., J. Org. Chem., Vol. 26, pp. 1097-1101 (1961); J. March, AdvancedOrganic Chemistry, 4th Edition, pp. 903 and 1091-1092, WileyInterscience (New York 1992); J. Crossley Maxwell, Aust. J. Chem., Vol.47, pp. 723-738 (1994); V. J. Wotring et al., Analytical Chemistry, Vol.62, No. 14, pp. 1506-1510 (1990); Tabushi et al., J. Am. Chem. Soc.,Vol. 103, pp. 6152-6157 (1981); T. Giorgi et al., “Gel-likelyomesophases formed in organic solvents by self-assembled guanineribbons,” Chemistry—A European Journal (2002), 8(9), 2143-2152; T.Suyamaet al., “A method for the preparation of substituted biguanides,”Nippon Kagaku Kaishi (1989), (5), 884-7; Polish Patent Publication PL148060 Bi; Polish Patent Publication PL 134682 Bi; C. S. Snijder et al.,Chem. Eur. J., Vol. 1, No. 9, pp. 594-597 (1995); S. Senda et al., GifuColl. Pharm., Gifu, Japan. Yakugaku Zasshi (1969), 89 (2), 254259; B.Gluncic et al, Acta Pharm. Jugosl. (1986), 36(4), 393-404; CanadianPatent Publication CA941377; M. Klein, Recent Dev. Mass Spectrom.Biochem. Med., [Proc. Int. Symp.], 4^(th) (1978), Meeting Date 1977, 1,471-82; PCT Patent Publication WO/9011283; Japanese Patent PublicationJP 62181279; T. Wada et al., “A New Boranophosphorylation Reaction forthe Synthesis of Deoxyribonucleoside Boranophosphates,” TetrahedronLetters, Vol. 43, No. 23, pp. 4137-4140 (2002); R. Schirrmacher et al.,“Dimethylpyridin-4-ylamine-catalysed alcoholysis of2-amino-N,N,N-trimethyl-9H-purine-6-ylammonium chloride: An effectiveroute to O6-substituted guanine derivatives from alcohols with poornucleophilicity,” Synthesis, Vol. 4, pp. 538-542 (2002); Z. Situ,“Synthesis of Tricyclic Derivatives of Guanine Analogue Catalyzed byKF-Al₂O₃ ,” Huaxue Shiji, Vol. 24, No. 1, p. 57 (2002); Korean Patent2000003081 (Korean Patent Application KR 1998-24185); S. Bailey et al.,“Synthesis and Antiviral Activity of 9-Alkoxypurines: New9-(Hydroxyalkoxy) Derivatives of Guanine and 8-Methylguanine,” AntiviralChem. Chemother., Vol. 5, No. 1, pp. 21-33 (1994); Japanese PatentPublication JP 06157529; Japanese Patent Publication JP 3217541; M. R.Harnden et al., “Synthesis, Oral Bioavailability and In Vivo Activity ofAcetal Derivatives of the Selective Antiherpesvirus Agent9-(3-Hydroxypropoxy)Guanine (BRL44385),” Antiviral Chem. Chemother.,Vol. 5, No. 3, pp. 147-54 (1994); Spanish Patent Publication ES 2047457;B. K. Bhattacharya et al., “Synthesis of Certain N- and C-alkyl PurineAnalogs,” J. Heterocycl. Chem., Vol. 30, No. 5, pp. 1341-9 (1993);Polish Patent Publication PL 148969; PCT Patent Publication WO/9011283;U.S. Pat. No. 5,298,618 (Speranza et al.); and Japanese PatentPublication JP 62181279, the disclosures of each of which are totallyincorporated herein by reference.

[0039] While known compositions and processes are suitable for theirintended purposes, a need remains for phase change inks that aresuitable for hot melt ink jet printing processes, such as hot meltpiezoelectric ink jet printing processes and the like. In addition, aneed remains for phase change inks that generate images with reductionin waxy texture and feel. Further, a need remains for phase change inksthat generate images with improved rub and scratch resistance.Additionally, a need remains for phase change inks that generate imageswith improved smear resistance. There is also a need for phase changeinks with desirably low viscosity values at the jetting temperature of ahot melt ink jet printer. In addition, there is a need for phase changeinks that generate images with improved image permanence. Further, thereis a need for phase change inks that generate images with improvedadhesion to print substrates such as paper and transparency material.Additionally, there is a need for phase change inks that can be fused ortransfused to substrates at relatively high temperatures, therebyenabling better control of the fusing process and better penetration ofthe inks into the final recording substrates.

SUMMARY OF THE INVENTION

[0040] The present invention is directed to compounds of the formulae

[0041] wherein Z is a group of the formula —OR₁, a group of the formula—SR₁, or a group of the formula —NR₁R₂, Y is a group of the formula—OR₃, a group of the formula —SR₃, or a group of the formula —NR₃R₄, nis an integer representing the number of repeat —(CH₂)— or —(CH₂CH₂O)—units, wherein, provided that at least one of R₁, R₂, R₃, R₄, R₅, and R₆is a hydrogen atom, provided that at least one of R₁, R₂, R₃, R₄, R₅,and R₆ is other than a hydrogen atom, and provided that at least one Zor Y within the compound is a group of the formula —NR₁R₂ or a group ofthe formula —NR₃R₄, R₁, R₂, R₃, R₄, R₅, R₆, and R₇ each, independentlyof the others, is (i) a hydrgen atom, (ii) an alkyl group, (iii) an arylgroup, (iv) an arylalkyl group, or (v) an alkylaryl group, and whereinR₇ can also be (vi) an alkoxy group, (vii) an aryloxy group, (viii) anarylalkyloxy group, (ix) an alkylaryloxy group, (x) a polyalkyleneoxygroup, (xi) a polyaryleneoxy group, (xii) a polyarylalkyleneoxy group,(xiii) a polyalkylaryleneoxy group, (xiv) a silyl alkylene group, (xvi)a polysilylene group, (xvii) a polysiloxane group, or (xviii) a group ofthe formula

[0042] wherein r is an integer representing a number of repeat —CH₂—groups, wherein s is an integer representing a number of repeating —CH₂—groups, and wherein X is (a) a direct bond, (b) an oxygen atom, (c) asulfur atom, (d) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogenatom, an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (e) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and wherein R₆ canalso be

[0043] Another embodiment of the present invention is directed to aphase change ink composition comprising a colorant and a phase changeink carrier comprising a material of this formula.

DETAILED DESCRIPTION OF THE INVENTION

[0044] The present invention is directed to compounds of the formulae

[0045] wherein Z is a group of the formula —OR₁, a group of the formula—SR₁, or a group of the formula —NR₁R₂, Y is a group of the formula—OR₃, a group of the formula —SR₃, or a group of the formula —NR₃R₄, nis an integer representing the number of repeat —(CH₂)— or —(CH₂CH₂O)—units, and typically is from 1 to about 100, although the value of n canbe outside of this range, wherein, provided that at least one of R₁, R₂,R₃, R₄, R₅, and R₆ is other than a hydrogen atom, and provided that atleast one Z or Y within the compound is a group of the formula —NR₁R₂ ora group of the formula —NR₃R₄, R₁, R₂, R₃, R₄, R₅, R₆, and R₇ each,independently of the others, provided that at least one of R₁, R₂, R₃,R₄, R₅, and R₆ is a hydrogen atom, is (i) a hydrogen atom, (ii) an alkylgroup (including linear, branched, saturated, unsaturated, cyclic,unsubstituted, and substituted alkyl groups, and wherein hetero atoms,such as oxygen, sulfur, nitrogen, silicon, phosphorus, or the like,either may or may not be placed between the carbon atoms in the alkylgroup), in one embodiment with at least about 1 carbon atom, in anotherembodiment with at least about 3 carbon atoms, and in yet anotherembodiment with at least about 8 carbon atoms, and in one embodimentwith no more than about 96 carbon atoms, in another embodiment with nomore than about 50 carbon atoms, and in yet another embodiment with nomore than about 24 carbon atoms, although the number of carbon atoms canbe outside of these ranges, (iii) an aryl group (including unsubstitutedand substituted aryl groups, and wherein hetero atoms, such as oxygen,sulfur, nitrogen, silicon, phosphorus, or the like, either may or maynot be present in the aryl group), in one embodiment with at least about6 carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 22 carbon atoms, inyet another embodiment with no more than about 18 carbon atoms, and instill another embodiment with no more than about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, (iv)an arylalkyl group (including unsubstituted and substituted arylalkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither or both of the alkyl portion and the aryl portion of thearylalkyl group), in one embodiment with at least about 7 carbon atoms,and in another embodiment with at least about 8 carbon atoms, and in oneembodiment with no more than about 96 carbon atoms, in anotherembodiment with no more than about 50 carbon atoms, in yet anotherembodiment with no more than about 24 carbon atoms, and in still anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, or (v) an alkylarylgroup (including unsubstituted and substituted alkylaryl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either orboth of the alkyl portion and the aryl portion of the alkylaryl group),in one embodiment with at least about 7 carbon atoms, and in anotherembodiment with at least about 8 carbon atoms, and in one embodimentwith no more than about 96 carbon atoms, in another embodiment with nomore than about 50 carbon atoms, in yet another embodiment with no morethan about 24 carbon atoms, and in still another embodiment with no morethan about 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, and wherein R₇ can also be (vi) an alkoxy group(including linear, branched, saturated, unsaturated, cyclic,unsubstituted, and substituted alkoxy groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the alkyl portion of the alkoxygroup), in one embodiment with at least about 1 carbon atom, in anotherembodiment with at least about 3 carbon atoms, and in yet anotherembodiment with at least about 8 carbon atoms, and in one embodimentwith no more than about 96 carbon atoms, in another embodiment with nomore than about 50 carbon atoms, and in yet another embodiment with nomore than about 24 carbon atoms, although the number of carbon atoms canbe outside of these ranges, (vii) an aryloxy group (includingunsubstituted and substituted aryloxy groups, and wherein hetero atoms,such as oxygen, sulfur, nitrogen, silicon, phosphorus, or the like,either may or may not be present in the aryl portion of the aryloxygroup), in one embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 22 carbon atoms, in yet anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (viii) an arylalkyloxygroup (including unsubstituted and substituted arylalkyloxy groups, andwherein hetero atoms, such as oxygen, sulfur, nitrogen, silicon,phosphorus, or the like, either may or may not be present in either orboth of the alkyl portion and the aryl portion of the arylalkyloxygroup), in one embodiment with at least about 7 carbon atoms, and inanother embodiment with at least about 8 carbon atoms, and in oneembodiment with no more than about 96 carbon atoms, in anotherembodiment with no more than about 50 carbon atoms, in yet anotherembodiment with no more than about 24 carbon atoms, and in still anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (ix) an alkylaryloxygroup (including unsubstituted and substituted alkylaryloxy groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either orboth of the alkyl portion and the aryl portion of the alkylaryloxygroup), in one embodiment with at least about 7 carbon atoms, and inanother embodiment with at least about 8 carbon atoms, and in oneembodiment with no more than about 96 carbon atoms, in anotherembodiment with no more than about 50 carbon atoms, in yet anotherembodiment with no more than about 24 carbon atoms, and in still anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (x) a polyalkyleneoxygroup, wherein the alkyl portion of the repeat alkyleneoxy groupstypically has from about 1 to about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as apolyethyleneoxy group, a polypropyleneoxy group, a polybutyleneoxygroup, or the like, and wherein the number of repeat alkyleneoxy groupstypically is from about 2 to about 50 repeat alkyleneoxy groups,although the number of repeat units can be outside of these ranges, (xi)a polyaryleneoxy group, wherein the aryl portion of the repeataryleneoxy groups typically has from about 6 to about 14 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas a polyphenyleneoxy group, a polynaphthaleneoxy group, apolyphenanthreneoxy group, or the like, and wherein the number of repeataryleneoxy groups typically is from about 2 to about 20 repeataryleneoxy groups, although the number of repeat units can be outside ofthese ranges, (xii) a polyarylalkyleneoxy group, wherein the arylalkylportion of the repeat arylalkyleneoxy groups typically has from about 7to about 50 carbon atoms, although the number of carbon atoms can beoutside of these ranges, such as a polybenzyleneoxy group, apolyphenylethyleneoxy group, or the like, and wherein the number ofrepeat arylalkyleneoxy groups typically is from about 2 to about 20repeat arylalkyleneoxy groups, although the number of repeat units canbe outside of these ranges, (xiii) a polyalkylaryleneoxy group, whereinthe alkylaryl portion of the repeat alkylaryleneoxy groups typically hasfrom about 7 to about 50 carbon atoms, although the number of carbonatoms can be outside of these ranges, such as a polytolueneoxy group orthe like, and wherein the number of repeat alkylaryleneoxy groupstypically is from about 2 to about 20 repeat alkylaryleneoxy groups,although the number of repeat units can be outside of these ranges,(xiv) a silyl group (including unsubstituted and substituted silylgroups), (xv) a siloxane group (including unsubstituted and substitutedsiloxane groups), (xvi) a polysilylene group (including unsubstitutedand substituted polysilylene groups), typically with from 2 to about 100repeat silylene units, although the number of repeat silylene units canbe outside of this range, (xvii) a polysiloxane group (includingunsubstituted and substituted polysiloxane groups), typically with from2 to about 200 repeat siloxane units, although the number of repeatsiloxane units can be outside of this range, or (xviii) a group of theformula

[0046] wherein r is an integer representing the number of repeat —CH₂—groups, in one embodiment being at least 1, in another embodiment atleast about 5, and in yet another embodiment at least about 10, and inone embodiment being no more than about 100, in another embodiment nomore than about 50, and in yet another embodiment no more than about 25,although the value of r can be outside of these ranges, wherein s is aninteger representing the number of repeating —CH₂— groups, in oneembodiment being at least 1, in another embodiment at least about 5, andin yet another embodiment at least about 10, and in one embodiment beingno more than about 100, in another embodiment no more than about 50, andin yet another embodiment no more than about 25, although the value of scan be outside of these ranges, and wherein X is (a) a direct bond, (b)an oxygen atom, (c) a sulfur atom, (d) a group of the formula —NR₄₀—wherein R₄₀ is a hydrogen atom, an alkyl group (including linear,branched, saturated, unsaturated, cyclic, unsubstituted, and substitutedalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not beplaced between the carbon atoms in the alkyl group), typically with from1 to about 50 carbon atoms, preferably with from about 2 to about 20carbon atoms, and more preferably with from about 4 to about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges, an aryl group (including unsubstituted and substituted arylgroups, and wherein hetero atoms, such as oxygen, sulfur, nitrogen,silicon, phosphorus, or the like, either may or may not be present inthe aryl group), typically with from about 6 to about 50 carbon atoms,preferably with from about 6 to about 20 carbon atoms, and morepreferably with from about 6 to about 10 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, an arylalkylgroup (including unsubstituted and substituted arylalkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either orboth of the alkyl portion and the aryl portion of the arylalkyl group),typically with from about 7 to about 100 carbon atoms, preferably withfrom about 7 to about 50 carbon atoms, and more preferably with fromabout 7 to about 20 carbon atoms, although the number of carbon atomscan be outside of these ranges, or an alkylaryl group (includingunsubstituted and substituted alkylaryl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either or both of the alkylportion and the aryl portion of the alkylaryl group), typically withfrom about 7 to about 100 carbon atoms, preferably with from about 7 toabout 50 carbon atoms, and more preferably with from about 7 to about 20carbon atoms, although the number of carbon atoms can be outside ofthese ranges, or (e) a group of the formula —CR₅₀R₆₀— wherein R₅₀ andR₆₀ each, independently of the other, is a hydrogen atom, an alkyl group(including linear, branched, saturated, unsaturated, cyclic,unsubstituted, and substituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be placed between the carbon atoms in the alkylgroup), typically with from 1 to about 50 carbon atoms, preferably withfrom about 2 to about 20 carbon atoms, and more preferably with fromabout 4 to about 12 carbon atoms, although the number of carbon atomscan be outside of these ranges, an aryl group (including unsubstitutedand substituted aryl groups, and wherein hetero atoms, such as oxygen,sulfur, nitrogen, silicon, phosphorus, or the like, either may or maynot be present in the aryl group), typically with from about 6 to about50 carbon atoms, preferably with from about 6 to about 20 carbon atoms,and more preferably with from about 6 to about 10 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, an arylalkylgroup (including unsubstituted and substituted arylalkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either orboth of the alkyl portion and the aryl portion of the arylalkyl group),typically with from about 7 to about 100 carbon atoms, preferably withfrom about 7 to about 50 carbon atoms, and more preferably with fromabout 7 to about 20 carbon atoms, although the number of carbon atomscan be outside of these ranges, or an alkylaryl group (includingunsubstituted and substituted alkylaryl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either or both of the alkylportion and the aryl portion of the alkylaryl group), typically withfrom about 7 to about 100 carbon atoms, preferably with from about 7 toabout 50 carbon atoms, and more preferably with from about 7 to about 20carbon atoms, although the number of carbon atoms can be outside ofthese ranges, and wherein R₆ can also be

[0047] wherein the substituents on the substituted alkyl, aryl,arylalkyl, alkylaryl, alkoxy, aryloxy, arylalkyloxy, alkylaryloxy,silyl, siloxane, polysilylene, and polysiloxane groups can be (but arenot limited to) hydroxy groups, halogen atoms, amine groups, iminegroups, ammonium groups, pyridine groups, pyridinium groups, ethergroups, aldehyde groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfide groups,sulfoxide groups, phosphine groups, phosphonium groups, phosphategroups, nitrile groups, mercapto groups, nitro groups, nitroso groups,sulfone groups, acyl groups, acid anhydride groups, azide groups, azogroups, cyanato groups, isocyanato groups, thiocyanato groups,isothiocyanato groups, alkoxy groups wherein the alkyl portion thereofis defined as alkyl is defined for R₁, aryloxy groups wherein the arylportion thereof is defined as aryl is defined for R₁, arylalkyloxygroups wherein the arylalkyl portion thereof is defined as arylalkyl isdefined for R₁, alkylaryloxy groups wherein the alkylaryl portionthereof is defined as alkylaryl is defined for R₁, polyalkyleneoxygroups, wherein the alkyl portion of the repeat alkyleneoxy groupstypically has from about 1 to about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as apolyethyleneoxy group, a polypropyleneoxy group, a polybutyleneoxygroup, or the like, and wherein the number of repeat alkyleneoxy groupstypically is from about 2 to about 50 repeat alkyleneoxy groups,although the number of repeat units can be outside of these ranges,polyaryleneoxy groups, wherein the aryl portion of the repeat aryleneoxygroups typically has from about 6 to about 14 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as apolyphenyleneoxy group, a polynaphthaleneoxy group, apolyphenanthreneoxy group, or the like, and wherein the number of repeataryleneoxy groups typically is from about 2 to about 20 repeataryleneoxy groups, although the number of repeat units can be outside ofthese ranges, polyarylalkyleneoxy groups, wherein the arylalkyl portionof the repeat arylalkyleneoxy groups typically has from about 7 to about50 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polybenzyleneoxy group, a polyphenylethyleneoxygroup, or the like, and wherein the number of repeat arylalkyleneoxygroups typically is from about 2 to about 20 repeat arylalkyleneoxygroups, although the number of repeat units can be outside of theseranges, polyalkylaryleneoxy group, wherein the alkylaryl portion of therepeat alkylaryleneoxy groups typically has from about 7 to about 50carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polytolueneoxy group or the like, and whereinthe number of repeat alkylaryleneoxy groups typically is from about 2 toabout 20 repeat alkylaryleneoxy groups, although the number of repeatunits can be outside of these ranges, silyl groups, siloxane groups,polysilylene groups, typically with from 2 to about 100 repeat silyleneunits, although the number of repeat silylene units can be outside ofthis range, polysiloxane groups, typically with from 2 to about 200repeat siloxane units, although the number of repeat siloxane units canbe outside of this range, mixtures thereof, and the like, wherein two ormore substituents can be joined together to form a ring.

[0048] In a specific embodiment, the compounds of the present inventionare nonpolymeric.

[0049] Some specific examples of R₁ include hydrogen, groups of theformula —(CH₂)_(n)CH₃ wherein n is an integer of from 0 to about 40,such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl (also calledarachidyl), and the like.

[0050] Some specific examples of R₂ include hydrogen, groups of theformula —(CH₂)_(n)CH₃ wherein n is an integer of from 0 to about 40,such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl (also calledarachidyl), and the like.

[0051] Some specific examples of R₃ include hydrogen, groups of theformula —(CH₂)_(n)CH₃ wherein n is an integer of from 0 to about 40,such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl (also calledarachidyl), and the like.

[0052] Some specific examples of R₄ include hydrogen, groups of theformula —(CH₂)_(n)CH₃ wherein n is an integer of from 0 to about 40,such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl (also calledarachidyl), and the like.

[0053] Some specific examples of R₅ include hydrogen and the like.

[0054] Some specific examples of R₆ include hydrogen,

[0055] and the like.

[0056] Some specific examples of “n” include 1, 3, 5, 7, 9, and thelike.

[0057] Some specific examples of compounds according to the presentinvention include

[0058] and the like, as well as mixtures thereof.

[0059] These materials can be prepared by any desired or suitableprocess. Another embodiment of the present invention is directed to aprocess for preparing a compound of the formula

[0060] wherein Z is a group of the formula —OR₁, a group of the formula—SR₁, or a group of the formula —NR₁R₂, Y is a group of the formula—OR₃, a group of the formula —SR₃, or a group of the formula —NR₃R₄, nis an integer representing the number of repeat —(CH₂)— or —(CH₂CH₂O)—units, wherein, provided that at least one of R₁, R₂, R₃, R₄, and R₆ isa hydrogen atom, provided that at least one of R₁, R₂, R₃, R₄, and R₆ isother than a hydrogen atom, and provided that at least one Z or Y withinthe compound is a group of the formula —NR₁R₂ or a group of the formula—NR₃R₄, R₁, R₂, R₃, R₄, R₆, and R₇ each, independently of the others, is(i) a hydrogen atom, (ii) an alkyl group, (iii) an aryl group, (iv) anarylalkyl group, or (v) an alkylaryl group, and wherein R₇ can also be(vi) an alkoxy group, (vii) an aryloxy group, (viii) an arylalkyloxygroup, (ix) an alkylaryloxy group, (x) a polyalkyleneoxy group, (xi) apolyaryleneoxy group, (xii) a polyarylalkyleneoxy group, (xiii) apolyalkylaryleneoxy group, (xiv) a silyl group, (xv) a siloxane group,(xvi) a polysilylene group, (xvii) a polysiloxane group, or (xviii) agroup of the formula

[0061] wherein r is an integer representing a number of repeat —CH₂—groups, wherein s is an integer representing a number of repeating —CH₂—groups, and wherein X is (a) a direct bond, (b) an oxygen atom, (c) asulfur atom, (d) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogenatom, an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (e) a group of the formula —CR₅OR₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and wherein R₆ canalso be

[0062] which comprises (I) admixing a compound of the formula

[0063] with a cyanuric halide at a temperature below about 0° C.; and(II) thereafter adding thereto one or more amines of the formulae R₁R₂NHand R₃R₄NH, wherein R₁, R₂, R₃, and R₄ can be either the same as eachother or different from each other and allowing the reactants to reactat a temperature of at least about 60° C., thereby generating a compoundof the formula

[0064] More specifically, compounds of the formulae

[0065] can be prepared from the corresponding amines. The reaction willbe illustrated with the compound of the formula

[0066] it is to be understood that the compounds of the other fourformulae can be made by analogous methods.

[0067] An amine compound of the formula

[0068] is reacted with a cyanuric halide, such as cyanuric chloride,cyanuric bromide, or the like, at reduced temperatures in an optionalsolvent. Thereafter, the amine or mixture of amines corresponding to thedesired R group(s) is added to the reaction mixture and the reactionmixture is heated at reflux, as follows:

[0069] The compound of the formula

[0070] and the cyanuric halide are present in any desired or effectiverelative amounts, in one embodiment at least about 4 moles of cyanurichalide per every one mole of

[0071] in another embodiment at least about 4.4 moles of cyanuric halideper every one mole of

[0072] and in yet another embodiment at least about 5 moles of cyanurichalide per every one mole of

[0073] and in one embodiment no more than about 8 moles of cyanurichalide per every one mole of

[0074] in another embodiment no more than about 6 moles of cyanurichalide per every one mole of

[0075] and in another embodiment no more than about 4 moles of cyanurichalide per every one mole of

[0076] although the relative amounts can be outside of these ranges.

[0077] When R₆ is not hydrogen, and if R₆ is an electron withdrawinggroup, the reaction with the cyanuric halide may also be assisted by thepresence of a strong non-nucleophilic base, such as sodium hydride(NaH). This strong non-nucleophilic base is added to the reactionmixture containing the compound of the formula

[0078] and the cyanuric halide in any desired or effective amount; forexample, if it is desired to substitute each hydrogen atom on the —NHR₆group with the triazine moiety, then about one molar equivalent ofstrong non-nucleophilic base is added for every —NHR₆ group desired tobe substituted with the triazine moiety—for example, four equivalents inthe reaction

[0079] The cyanuric halide and the compound of the formula

[0080] can be present in an optional solvent. Any desired or effectivesolvent can be used, such as tetrahydrofuran, dioxane, acetonitrile,toluene, benzene, dimethylformamide, mixtures thereof, or the like. Whenused, the solvent is present in any desired or effective amount, in oneembodiment at least about 2 liters of solvent per every one mole of

[0081] in another embodiment at least about 3 liters of solvent perevery one mole of

[0082] and in yet another embodiment at least about 4 liters of solventper every one mole of

[0083] and in one embodiment no more than about 10 liters of solvent perevery one mole of

[0084] in another embodiment no more than about 8 liters of solvent perevery one mole of

[0085] and in yet another embodiment no more than about 6 liters ofsolvent per every one mole of

[0086] although the amount of solvent can be outside of these ranges.

[0087] The reaction mixture containing the cyanuric halide and thecompound of the formula

[0088] is cooled to any desired or effective temperature, in oneembodiment about −78° C., in another embodiment about −10° C., and inyet another embodiment about 0° C., although the temperature can beoutside of these ranges.

[0089] The reaction mixture containing the compound of the formula

[0090] and the cyanuric halide is then allowed to warm to roomtemperature (typically about 20° C.).

[0091] Thereafter, the amine or mixture of amines corresponding to thedesired R group(s) is added to the reaction mixture and the reactionmixture is heated at reflux. The amine or mixture of amines is presentin any desired or effective relative amounts, in one embodiment at leastabout 8 moles of amine(s) per every one mole of

[0092] in another embodiment at least about 16 moles of amine(s) perevery one mole of

[0093] and in yet another embodiment at least about 24 moles of amine(s)per every one mole of

[0094] and in one embodiment no more than about 32 moles of amine(s) perevery one mole of

[0095] and in another embodiment no more than about 24 moles of amine(s)per every one mole of

[0096] although the relative amounts can be outside of these ranges.

[0097] The reaction mixture containing the amine or mixture of amines isheated to any desired or effective temperature, in one embodiment atleast about 60° C., in another embodiment at least about 80° C., and inyet another embodiment at least about 100° C., and in one embodiment nomore than about 180° C., in another embodiment no more than about 160°C., and in yet another embodiment no more than about 120° C., althoughthe temperature can be outside of these ranges.

[0098] The reaction mixture is allowed to heat at reflux for any desiredor effective period of time, in one embodiment at least about 60minutes, in another embodiment at least about 90 minutes, and in yetanother embodiment at least about 120 minutes, and in one embodiment nomore than about 600 minutes, in another embodiment no more than about540 minutes, and in yet another embodiment no more than about 480minutes, although the time can be outside of these ranges.

[0099] Subsequent to completion of the reaction, the product can bepurified.

[0100] Compounds of the formulae

[0101] can also, be prepared by a two step process in which thecorresponding amine is first converted to a 2,4-dichloro-1,3,5-triazinederivative and the 2,4-dichloro-1,3,5-triazine derivative is thenconverted to the desired compound. The reaction will be illustrated withthe compound of the formula

[0102] it is to be understood that the compounds of the other fourformulae can be made by analogous methods.

[0103] A amine compound of the formula

[0104] is reacted with a cyanuric halide, such as cyanuric chloride,cyanuric bromide, or the like, at reduced temperatures in an optionalsolvent, followed by reaction with a base, such as sodium carbonate,potassium carbonate, sodium hydroxide, potassium hydroxide,triethylamine, pyridine, diisopropylethylamine, mixtures thereof, or thelike, as follows:

[0105] The compound of the formula

[0106] and the cyanuric halide are present in any desired or effectiverelative amounts, in one embodiment at least about 4 moles of cyanurichalide per every one mole of

[0107] in another embodiment at least about 4.4 moles of cyanuric halideper every one mole of

[0108] and in yet another embodiment at least about 5 moles of cyanurichalide per every one mole of

[0109] and in one embodiment no more than about 8 moles of cyanurichalide per every one mole of

[0110] in another embodiment no more than about 6 moles of cyanurichalide per every one mole of

[0111] and in another embodiment no more than about 4 moles of cyanurichalide per every one mole of

[0112] although the relative amounts can be outside of these ranges.

[0113] When R₆ is not hydrogen, and if R₆ is an electron withdrawinggroup, the reaction with the cyanuric halide may also be assisted by thepresence of a strong non-nucleophilic base, such as sodium hydride(NaH). This strong non-nucleophilic base is added to the reactionmixture containing the compound of the formula

[0114] and the cyanuric halide in any desired or effective amount; forexample, if it is desired to substitute each hydrogen atom on the —NHR₆group with the triazine moiety, then about one molar equivalent ofstrong non-nucleophilic base is added for every —NHR₆ group desired tobe substituted with the triazine moiety—for example, four equivalents inthe reaction

[0115] The cyanuric halide and the compound of the formula

[0116] can be present in an optional solvent. Any desired or effectivesolvent can be used, such as tetrahydrofuran, acetone, dioxane, toluene,benzene, acetonitrile, mixtures thereof, or the like. When present, thesolvent is present in any desired or effective amount, in one embodimentat least about 2 liters of solvent per every one mole of

[0117] in another embodiment at least about 3 liters of solvent perevery one mole of

[0118] and in yet another embodiment at least about 4 liters of solventper every one mole of

[0119] and in one embodiment no more than about 10 liters of solvent perevery one mole of

[0120] in another embodiment no more than about 9 liters of solvent perevery one mole of

[0121] and in yet another embodiment no more than about 8 liters ofsolvent per every one mole of

[0122] although the amount of solvent can be outside of these ranges.

[0123] The reaction mixture containing the cyanuric halide and thecompound of the formula

[0124] is cooled to any desired or effective temperature, in oneembodiment about −78° C., in another embodiment about −10° C., and inyet another embodiment about 0° C., although the temperature can beoutside of these ranges.

[0125] The reaction mixture containing the cyanuric halide and thecompound of the formula

[0126] is maintained at the cooled temperature for any desired oreffective period of time, in one embodiment for at least about 5minutes, in another embodiment for at least about 10 minutes, and in yetanother embodiment for at least about 20 minutes, and in one embodimentfor no more than about 600 minutes, in another embodiment for no morethan about 540 minutes, and in yet another embodiment for no more thanabout 480 minutes, although the time can be outside of these ranges.

[0127] Thereafter, the reaction mixture is added with the base to coldwater to precipitate the desired product. The base can be present in anydesired or effective amount, in one embodiment at least about 4 moles ofbase per every one mole of

[0128] in another embodiment at least about 5 moles of base per everyone mole of

[0129] and in yet another embodiment at least about 6 moles of base perevery one mole of

[0130] and in one embodiment no more than about 24 moles of base perevery one mole of

[0131] in another embodiment no more than about 16 moles of base perevery one mole of

[0132] and in another embodiment no more than about 8 moles of base perevery one mole of

[0133] although the relative amounts can be outside of these ranges.

[0134] Subsequent to completion of the reaction, the product can bepurified.

[0135] The product thus prepared is of the formula

[0136] This compound is then reacted with the amine or mixture of aminescorresponding to the desired R group(s) at reflux to give the desiredcompound according to the present invention, as follows:

[0137] The amine or mixture of amines is present in any desired oreffective relative amounts, in one embodiment at least about 8 moles ofamine(s) per every one mole of

[0138] in another embodiment at least about 16 moles of amine(s) perevery one mole of

[0139] and in yet another embodiment at least about 24 moles of amine(s)per every one mole of

[0140] and in one embodiment no more than about 36 moles of amine(s) perevery one mole of

[0141] and in another embodiment no more than about 24 moles of amine(s)per every one mole of

[0142] although the relative amounts can be outside of these ranges.

[0143] The amine(s) and the compound of the formula

[0144] can be present in an optional solvent. Any desired or effectivesolvent can be used, such as dioxane, tetrahydrofuran,dimethylformamide, benzene, toluene, acetonitrile, mixtures thereof, orthe like. When present, the solvent is present in any desired oreffective amount, in one embodiment at least about 2 liters of solventper every one mole of

[0145] in another embodiment at least about 3 liters of solvent perevery one mole of

[0146] and in yet another embodiment at least about 4 liters of solventper every one mole of

[0147] and in one embodiment no more than about 12 liters of solvent perevery one mole of

[0148] in another embodiment no more than about 11 liters of solvent perevery one mole of

[0149] and in yet another embodiment no more than about 10 liters ofsolvent per every one mole of

[0150] although the amount of solvent can be outside of these ranges.

[0151] The reaction mixture containing the amine or mixture of aminesand the compound of the formula

[0152] is heated to any desired or effective temperature, in oneembodiment at least about 60° C., in another embodiment at least about80° C., and in yet another embodiment at least about 100° C., and in oneembodiment no more than about 180° C., in another embodiment no morethan about 160° C., and in yet another embodiment no more than about140° C., although the temperature can be outside of these ranges.

[0153] The reaction mixture is allowed to heat at reflux for any desiredor effective period of time, in one embodiment at least about 30minutes, in another embodiment at least about 60 minutes, and in yetanother embodiment at least about 90 minutes, and in one embodiment nomore than about 600 minutes, in another embodiment no more than about540 minutes, and in yet another embodiment no more than about 480minutes, although the time can be outside of these ranges.

[0154] Subsequent to completion of the reaction, the product can bepurified.

[0155] Starting materials such as

[0156] can be prepared as described in Parts A through D of Example Ihereinbelow, or as described in, for example, U.S. Pat. No. 2,703,808;M. F. Shostakovskii et al., Zhurnal Obshchei Khimii, Vol. 35, p. 804(1965); and J. N. Ashley et al., J. Chem. Soc., 1958, p. 3293, thedisclosures of each of which are totally incorporated herein byreference.

[0157] Another embodiment of the present invention is directed to aprocess for preparing a compound of the formula

[0158] wherein n is an integer representing the number of repeat —(CH₂)—or —(CH₂CH₂O)— units, wherein, provided that at least one of R₁, R₂, R₃,R₄, and R₅ is a hydrogen atom, provided that at least one of R₁, R₂, R₃,R₄, and R₅ is other than a hydrogen atom, R₁, R₂, R₃, R₄, R₅, and R₇each, independently of the others, is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup, and wherein R₇ can also be (vi) an alkoxy group, (vii) an aryloxygroup, (viii) an arylalkyloxy group, (ix) an alkylaryloxy group, (x) apolyalkyleneoxy group, (xi) a polyaryleneoxy group, (xii) apolyarylalkyleneoxy group, (xiii) a polyalkylaryleneoxy group, (xiv) asilyl group, (xv) a siloxane group, (xvi) a polysilylene group, (xvii) apolysiloxane group, or (xviii) a group of the formula

[0159] wherein r is an integer representing a number of repeat —CH₂—groups, wherein s is an integer representing a number of repeating —CH₂—groups, and wherein X is (a) a direct bond, (b) an oxygen atom, (c) asulfur atom, (d) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogenatom, an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (e) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group which comprises (I)admixing a compound of the formula

[0160] with a phosgenating agent and a non-nucleophilic base at atemperature below about 0° C.; and (II) thereafter adding thereto one ormore amines of the formulae R₁R₂NH and R₃R₄NH, wherein R₁, R₂, R₃, andR₄ can be either the same as each other or different from each other andallowing the reactants to react at a temperature of at least about 60°C., thereby generating a compound of the formula

[0161] More specifically, compounds of the formulae

[0162] can be prepared from the corresponding amines. The reaction willbe illustrated with the compound of the formula

[0163] it is to be understood that the compounds of the other fourformulae can be made by analogous methods.

[0164] An amine compound of the formula

[0165] is first made to react with a phosgenating agent, such asphosgene, diphosgene, triphosgene, mixtures thereof, or the like, and anon-nucleophilic base, such as triethylamine, diisopropylethylamine,pyridine, mixtures thereof, or the like, in the presence of an optionalsolvent at reduced temperatures. Thereafter, the reaction mixture iswarmed and the amine or mixture of amines corresponding to the desired Rgroups is added to the reaction mixture and the mixture is furtherheated, as follows:

[0166] and the phosgenating agent are present in any desired oreffective relative amounts, in one embodiment at least about 0.66 moleof phosgenating agent per every one mole of

[0167] in another embodiment at least about 0.75 mole of phosgenatingagent per every one mole of

[0168] and in yet another embodiment at least about 0.8 mole ofphosgenating agent per every one mole of

[0169] and in one embodiment no more than about 1 mole of phosgenatingagent per every one mole of

[0170] although the relative amounts can be outside of these ranges.

[0171] The compound of the formula

[0172] and the base are present in any desired or effective relativeamounts, in one embodiment at least about 4 moles of base per every onemole of

[0173] in another embodiment at least about 4.5 moles of base per everyone mole of

[0174] and in yet another embodiment at least about 5 moles of base perevery one mole of

[0175] and in one embodiment no more than about 8 moles of base perevery one mole of

[0176] in another embodiment no more than about 7 moles of base perevery one mole of

[0177] and in yet another embodiment no more than about 6 moles of baseper every one mole of

[0178] although the relative amounts can be outside of these ranges.

[0179] The compound of the formula

[0180] the phosgenating agent, and the base can be made to react in anoptional solvent. Any desired or effective solvent can be used, such astetrahydrofuran, dioxane, benzene, toluene, dimethylformamide, mixturesthereof, or the like. When used, the solvent is present in any desiredor effective amount, in one embodiment at least about 2 liters ofsolvent per every one mole of

[0181] in another embodiment at least about 3 liters of solvent perevery one mole of

[0182] and in yet another embodiment at least about 4 liters of solventper every one mole of

[0183] and in one embodiment no more than about 12 liters of solvent perevery one mole of

[0184] in another embodiment no more than about 10 liters of solvent perevery one mole of

[0185] and in yet another embodiment no more than about 8 liters ofsolvent per every one mole of

[0186] although the amount of solvent can be outside of these ranges.

[0187] The reaction mixture containing the

[0188] the phosgenating agent, and the base is cooled to any desired oreffective temperature, in one embodiment about −78° C., in anotherembodiment about −10° C., and in yet another embodiment about 0° C.,although the temperature can be outside of these ranges.

[0189] The reaction mixture containing the

[0190] the phosgenating agent, and the base is then allowed to warm toroom temperature (typically about 20° C.).

[0191] Thereafter, the amine or mixture of amines corresponding to thedesired R group(s) is added to the reaction mixture and the reactionmixture is heated. The amine or mixture of amines is present in anydesired or effective relative amounts, in one embodiment at least about2 moles of amine(s) per every one mole of

[0192] in another embodiment at least about 2.5 moles of amine(s) perevery one mole of

[0193] and in yet another embodiment at least about 3 moles of amine(s)per every one mole of

[0194] and in one embodiment no more than about 6 moles of amine(s) perevery one mole of

[0195] in another embodiment no more than about 5 moles of amine(s) perevery one mole of

[0196] and in yet another embodiment no more than about 4 moles ofamine(s) per every one mole of

[0197] although the relative amounts can be outside of these ranges.

[0198] The reaction mixture containing the amine or mixture of amines isheated to any desired or effective temperature, in one embodiment atleast about 25° C., in another embodiment at least about 40° C., and inyet another embodiment at least about 50° C., and in one embodiment nomore than about 100° C., in another embodiment no more than about 80°C., and in yet another embodiment no more than about 60° C., althoughthe temperature can be outside of these ranges.

[0199] The reaction mixture is heated for any desired or effectiveperiod of time, in one embodiment at least about 5 minutes, in anotherembodiment at least about 20 minutes, and in yet another embodiment atleast about 30 minutes, and in one embodiment no more than about 300minutes, in another embodiment no more than about 240 minutes, and inyet another embodiment no more than about 180 minutes, although the timecan be outside of these ranges.

[0200] The reaction mixture can then be cooled to room temperature andadded to water to precipitate the product.

[0201] Subsequent to completion of the reaction, the product can bepurified.

[0202] Starting materials such as

[0203] can be prepared as described in Parts A and B of Example VIIIhereinbelow.

[0204] The ureas and the triaminotriazines in the phase change inkcarriers of the inks of the present invention form reversible hydrogenbonds, resulting in the formation of dimers, oligomers, polymers, orpolymer networks held together by hydrogen bonds instead of covalentbonds. An example of such bond formation is illustrated as follows:

[0205] While not being limited to any particular theory, it is believedthat in the inks of the present invention, some of these hydrogen bondscan be broken at the temperatures at which hot melt ink jet printingoccurs (typically, although not necessarily, over 100° C.). When the inkis printed onto an intermediate transfer member or a final recordingsubstrate, the ink cools as it is printed, which results in reformationof any hydrogen bonds broken by heating. The polymer-like materials thusformed behave like conventional covalently-bonded polymers to enhanceimage permanence.

[0206] The formation of hydrogen-bonded oligomers or polymers fromspecific ink carrier materials can be determined by any desired method.For example, a dramatic onset of resinous and viscoelasticcharacteristics on cooling is indicative of the formation ofhydrogen-bonded oligomers or polymers from the ink carrier material orcombination of materials. The formation of hydrogen bonds andhydrogen-bonded oligomers or polymers can also be detected by IRspectroscopy. NMR spectroscopy may also help to detect the presence ofhydrogen-bonded oligomers or polymers. In situations wherein the inkcarrier material is crystalline, X-ray crystallography can be used todefine the oligomeric or polymeric structure.

[0207] In the direct printing mode, the phase change carrier compositionin one embodiment contains one or more materials that enable the phasechange ink (1) to be applied in a thin film of uniform thickness on thefinal recording substrate (such as paper, transparency material, and thelike) when cooled to ambient temperature after printing directly to therecording substrate, (2) to be ductile while retaining sufficientflexibility so that the applied image on the substrate will not fractureupon bending, and (3) to possess a high degree of lightness, chroma,transparency, and thermal stability.

[0208] In an offset printing transfer or indirect printing mode, thephase change carrier composition in one embodiment exhibits not only thecharacteristics desirable for direct printing mode inks, but alsocertain fluidic and mechanical properties desirable for use in such asystem, as described in, for example, U.S. Pat. No. 5,389,958, thedisclosure of which is totally incorporated herein by reference.

[0209] In some embodiments of the present invention, the compound of thepresent invention functions as the sole phase change ink carrier for theink composition. In other embodiments, if desired, other phase changeink carrier materials can be present in combination with the compound ofthe present invention.

[0210] When the compounds of the present invention are present incombination with other phase change ink carrier materials, the compoundsof the formulae

[0211] are present in any desired or effective amount, in one embodimentat least about 0.1 percent by weight of the ink composition, in anotherembodiment at least about 1 percent by weight of the ink composition, inyet another embodiment at least about 5 percent by weight of the inkcomposition, and in still another embodiment at least about 10 percentby weight of the ink composition, and in one embodiment no more thanabout 40 percent by weight of the ink composition, in another embodimentno more than about 25 percent by weight of the ink composition, in yetanother embodiment no more than about 20 percent by weight of the inkcomposition, and in still another embodiment no more than about 15percent by weight of the ink composition, although the amount of thismaterial in the ink can be outside of these ranges.

[0212] When other phase change ink carrier materials are used incombination with the compounds of the present invention, any desired oreffective carrier composition can be used. Examples of suitable inkcarrier materials include fatty amides, such as monoamides,tetra-amides, mixtures thereof, and the like. Specific examples ofsuitable fatty amide ink carrier materials include stearyl stearamide, adimer acid based tetra-amide that is the reaction product of dimer acid,ethylene diamine, and stearic acid, a dimer acid based tetra-amide thatis the reaction product of dimer acid, ethylene diamine, and acarboxylic acid having at least about 36 carbon atoms, and the like, aswell as mixtures thereof. When the fatty amide ink carrier is a dimeracid based tetra-amide that is the reaction product of dimer acid,ethylene diamine, and a carboxylic acid having at least about 36 carbonatoms, the carboxylic acid is of the general formula

[0213] wherein R is an alkyl group, including linear, branched,saturated, unsaturated, and cyclic alkyl groups, said alkyl group in oneembodiment having at least about 36 carbon atoms, in another embodimenthaving at least about 40 carbon atoms, said alkyl group in oneembodiment having no more than about 200 carbon atoms, in anotherembodiment having no more than about 150 carbon atoms, and in yetanother embodiment having no more than about 100 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges. Carboxylicacids of this formula are commercially available from, for example,Baker Petrolite, Tulsa, Okla., and can also be prepared as described inExample 1 of U.S. Pat. No. 6,174,937, the disclosure of which is totallyincorporated herein by reference. Further information on fatty amidecarrier materials is disclosed in, for example, U.S. Pat. No. 4,889,560,U.S. Pat. No. 4,889,761, U.S. Pat. No. 5,194,638, U.S. Pat. No.4,830,671, U.S. Pat. No. 6,174,937, U.S. Pat. No. 5,372,852, U.S. Pat.No. 5,597,856, U.S. Pat. No. 6,174,937, and British Patent GB 2 238 792,the disclosures of each of which are totally incorporated herein byreference.

[0214] Also suitable as phase change ink carrier materials areisocyanate-derived resins and waxes, such as urethane isocyanate-derivedmaterials, urea isocyanate-derived materials, urethane/ureaisocyanate-derived materials, mixtures thereof, and the like. Furtherinformation on isocyanate-derived carrier materials is disclosed in, forexample, U.S. Pat. No. 5,750,604, U.S. Pat. No. 5,780,528, U.S. Pat. No.5,782,966, U.S. Pat. No. 5,783,658, U.S. Pat. No. 5,827,918, U.S. Pat.No. 5,830,942, U.S. Pat. No. 5,919,839, U.S. Pat. No. 6,255,432, U.S.Pat. No. 6,309,453, British Patent GB 2 294 939, British Patent GB 2 305928, British Patent GB 2 305 670, British Patent GB 2 290 793, PCTPublication WO 94/14902, PCT Publication WO 97/12003, PCT Publication WO97/13816, PCT Publication WO 96/14364, PCT Publication WO97/33943, andPCT Publication WO95/04760, the disclosures of each of which are totallyincorporated herein by reference.

[0215] Mixtures of fatty amide materials and isocyanate-derivedmaterials can also be employed as the ink carrier composition for inksof the present invention.

[0216] Additional suitable phase change ink carrier materials for thepresent invention include paraffins, microcrystalline waxes,polyethylene waxes, ester waxes, amide waxes, fatty acids, fattyalcohols, fatty amides and other waxy materials, sulfonamide materials,resinous materials made from different natural sources (such as, forexample, tall oil rosins and rosin esters), and many synthetic resins,oligomers, polymers and copolymers, such as ethylene/vinyl acetatecopolymers, ethylene/acrylic acid copolymers, ethylene/vinylacetate/acrylic acid copolymers, copolymers of acrylic acid withpolyamides, and the like, ionomers, and the like, as well as mixturesthereof. One or more of these materials can also be employed in amixture with a fatty amide material and/or an isocyanate-derivedmaterial.

[0217] In one specific embodiment, the phase change ink carriercomprises the ink carrier comprises (a) a polyethylene wax, present inthe ink in an amount in one embodiment of at least about 25 percent byweight of the ink, in another embodiment of at least about 30 percent byweight of the ink, and in yet another embodiment of at least about 37percent by weight of the ink, and in one embodiment of no more thanabout 60 percent by weight of the ink, in another embodiment of no morethan about 53 percent by weight of the ink, and in yet anotherembodiment of no more than about 48 percent by weight of the ink,although the amount can be outside of these ranges; (b) a stearylstearamide wax, present in the ink in an amount in one embodiment of atleast about 8 percent by weight of the ink, in another embodiment of atleast about 10 percent by weight of the ink, and in yet anotherembodiment of at least about 12 percent by weight of the ink, and in oneembodiment of no more than about 32 percent by weight of the ink, inanother embodiment of no more than about 28 percent by weight of theink, and in yet another embodiment of no more than about 25 percent byweight of the ink, although the amount can be outside of these ranges;(c) a dimer acid based tetra-amide that is the reaction product of dimeracid, ethylene diamine, and a carboxylic acid derivative of a long chainalcohol having greater than thirty six carbon atoms, present in the inkin an amount in one embodiment of at least about 10 percent by weight ofthe ink, in another embodiment of at least about 13 percent by weight ofthe ink, and in yet another embodiment of at least about 16 percent byweight of the ink, and in one embodiment of no more than about 32percent by weight of the ink, in another embodiment of no more thanabout 27 percent by weight of the ink, and in yet another embodiment ofno more than about 22 percent by weight of the ink, although the amountcan be outside of these ranges; (d) a urethane resin derived from thereaction of two equivalents of hydroabietyl alcohol and one equivalentof isophorone diisocyanate, present in the ink in an amount in oneembodiment of at least about 6 percent by weight of the ink, in anotherembodiment of at least about 8 percent by weight of the ink, and in yetanother embodiment of at least about 10 percent by weight of the ink,and in one embodiment of no more than about 16 percent by weight of theink, in another embodiment of no more than about 14 percent by weight ofthe ink, and in yet another embodiment of no more than about 12 percentby weight of the ink, although the amount can be outside of theseranges; (e) a urethane resin that is the adduct of three equivalents ofstearyl isocyanate and a glycerol-based alcohol, present in the ink inan amount in one embodiment of at least about 2 percent by weight of theink, in another embodiment of at least about 3 percent by weight of theink, and in yet another embodiment of at least about 4.5 percent byweight of the ink, and in one embodiment of no more than about 13percent by weight of the ink, in another embodiment of no more thanabout 10 percent by weight of the ink, and in yet another embodiment ofno more than about 7.5 percent by weight of the ink, although the amountcan be outside of these ranges; and (f) an antioxidant, present in theink in an amount in one embodiment of at least about 0.01 percent byweight of the ink, in another embodiment of at least about 0.05 percentby weight of the ink, and in yet another embodiment of at least about0.1 percent by weight of the ink, and in one embodiment of no more thanabout 1 percent by weight of the ink, in another embodiment of no morethan about 0.5 percent by weight of the ink, and in yet anotherembodiment of no more than about 0.3 percent by weight of the ink,although the amount can be outside of these ranges.

[0218] The ink carrier is present in the phase change ink of the presentinvention in any desired or effective amount, in one embodiment of atleast about 0.1 percent by weight of the ink, in another embodiment ofat least about 50 percent by weight of the ink, and in yet anotherembodiment of at least about 90 percent by weight of the ink, and in oneembodiment of no more than about 99 percent by weight of the ink, inanother embodiment of no more than about 98 percent by weight of theink, and in yet another embodiment of no more than about 95 percent byweight of the ink, although the amount can be outside of these ranges.

[0219] Any desired or effective colorant can be employed in the inks ofthe present invention, including dyes, pigments, mixtures thereof, andthe like, provided that the colorant can be dissolved or dispersed inthe phase change ink carrier. The phase change carrier compositions ofthe current invention can be used in combination with conventional phasechange ink colorant materials, such as Color Index (C.I.) Solvent Dyes,Disperse Dyes, modified Acid and Direct Dyes, Basic Dyes, Sulphur Dyes,Vat Dyes, and the like. Examples of suitable dyes include Neozapon Red492 (BASF); Orasol Red G (Ciba-Geigy); Direct Brilliant Pink B (Crompton& Knowles); Aizen Spilon Red C-BH (Hodogaya Chemical); Kayanol Red 3BL(Nippon Kayaku); Levanol Brilliant Red 3BW (Mobay Chemical); LevadermLemon Yellow (Mobay Chemical); Spirit Fast Yellow 3G; Aizen SpilonYellow C-GNH (Hodogaya Chemical); Sirius Supra Yellow GD 167; CartasolBrilliant Yellow 4GF (Sandoz); Pergasol Yellow CGP (Ciba-Geigy); OrasolBlack RLP (Ciba-Geigy); Savinyl Black RLS (Sandoz); Dermacarbon 2GT(Sandoz); Pyrazol Black BG (ICI); Morfast Black Conc. A(Morton-Thiokol); Diaazol Black RN Quad (ICI); Orasol Blue GN(Ciba-Geigy); Savinyl Blue GLS (Sandoz); Luxol Blue MBSN(Morton-Thiokol); Sevron Blue 5GMF (ICI); Basacid Blue 750 (BASF),Neozapon Black X51 [C.I. Solvent Black, C.I. 12195] (BASF), Sudan Blue670 [C.I. 61554] (BASF), Sudan Yellow 146 [C.I. 12700] (BASF), Sudan Red462 [C.I. 26050] (BASF), Intratherm Yellow 346 from Crompton andKnowles, C.I. Disperse Yellow 238, Neptune Red Base NB543 (BASF, C.I.Solvent Red 49), Neopen Blue FF-4012 from BASF, Lampronol Black BR fromICI (C.I. Solvent Black 35), Morton Morplas Magenta 36 (C.I. Solvent Red172), metal phthalocyanine colorants such as those disclosed in U.S.Pat. No. 6,221,137, the disclosure of which is totally incorporatedherein by reference, and the like. Polymeric dyes can also be used, suchas those disclosed in, for example, U.S. Pat. No. 5,621,022 and U.S.Pat. No. 5,231,135, the disclosures of each of which are totallyincorporated herein by reference, and commercially available from, forexample, Milliken & Company as Milliken Ink Yellow 869, Milliken InkBlue 92, Milliken Ink Red 357, Milliken Ink Yellow 1800, Milliken InkBlack 8915-67, uncut Reactant Orange X-38, uncut Reactant Blue X-17, anduncut Reactant Violet X-80.

[0220] Pigments are also suitable colorants for the phase change inks ofthe present invention. Examples of suitable pigments include VioletToner VT-8015 (Paul Uhlich); Paliogen Violet 5100 (BASF); PaliogenViolet 5890 (BASF); Permanent Violet VT 2645 (Paul Uhlich); HeliogenGreen L8730 (BASF); Argyle Green XP-111-S (Paul Uhlich); Brilliant GreenToner GR 0991 (Paul Uhlich); Lithol Scarlet D3700 (BASF); Toluidine Red(Aldrich); Scarlet for Thermoplast NSD PS PA (Ugine Kuhlmann of Canada);E. D. Toluidine Red (Aldrich); Lithol Rubine Toner (Paul Uhlich); LitholScarlet 4440 (BASF); Bon Red C (Dominion Color Company); Royal BrilliantRed RD-8192 (Paul Uhlich); Oracet Pink RF (Ciba-Geigy); Paliogen Red3871K (BASF); Paliogen Red 3340 (BASF); Lithol Fast Scarlet L4300(BASF); Heliogen Blue L6900, L7020 (BASF); Heliogen Blue K6902, K6910(BASF); Heliogen Blue D6840, D7080 (BASF); Sudan Blue OS (BASF); NeopenBlue FF4012 (BASF); PV Fast Blue B2G01 (American Hoechst); Irgalite BlueBCA (Ciba-Geigy); Paliogen Blue 6470 (BASF); Sudan III (Red Orange)(Matheson, Colemen Bell); Sudan II (Orange) (Matheson, Colemen Bell);Sudan Orange G (Aldrich), Sudan Orange 220 (BASF); Paliogen Orange 3040(BASF); Ortho Orange OR 2673 (Paul Uhlich); Paliogen Yellow 152, 1560(BASF); Lithol Fast Yellow 0991 K (BASF); Paliotol Yellow 1840 (BASF);Novoperm Yellow FGL (Hoechst); Permanent Yellow YE 0305 (Paul Uhlich);Lumogen Yellow D0790 (BASF); Suco-Yellow L1250 (BASF); Suco-Yellow D1355(BASF); Suco Fast Yellow D1355, D1351 (BASF); Hostaperm Pink E (AmericanHoechst); Fanal Pink D4830 (BASF); Cinquasia Magenta (Du Pont); PaliogenBlack L0084 (BASF); Pigment Black K801 (BASF); and carbon blacks such asREGAL 330® (Cabot), Carbon Black 5250, Carbon Black 5750 (ColumbiaChemical), and the like.

[0221] Also suitable as colorants are the isocyanate-derived coloredresins disclosed in U.S. Pat. No. 5,780,528, the disclosure of which istotally incorporated herein by reference.

[0222] Also suitable are the colorants disclosed in CopendingApplication U.S. Ser. No. 10/072,241, filed Feb. 8, 2002, entitled“Phthalocyanine Compositions,” Copending Application U.S. Ser. No.10/072,210, Feb. 8, 2002, entitled “Ink Compositions ContainingPhthalocyanines,” Copending Application U.S. Ser. No. 10/072,237, filedFeb. 8, 2002, entitled “Methods For Preparing PhthalocyanineCompositions,” Copending Application U.S. Ser. No. 10/185,261, filedJun. 27, 2002, entitled “Processes for Preparing DianthranilateCompounds and Diazopyridone Colorants,” Copending Application U.S. Ser.No. 10/185,994, filed Jun. 27, 2002, entitled “Dimeric Azo PyridoneColorants,” Copending Application U.S. Ser. No. 10/184,269, filed Jun.27, 2002, entitled “Phase Change Inks Containing Dimeric Azo PyridoneColorants,” Copending Application U.S. Ser. No. 10/185,264, filed Jun.27, 2002, entitled “Phase Change Inks Containing Azo PyridoneColorants,” Copending Application U.S. Ser. No. 10/186,024, filed Jun.27, 2002, entitled “Azo Pyridone Colorants,” Copending Application U.S.Ser. No. 10/185,597, filed Jun. 27, 2002, entitled “Process forPreparing Substituted Pyridone Compounds,” Copending Application U.S.Ser. No. 10/185,828, filed Jun. 27, 2002, entitled “Method for MakingDimeric Azo Pyridone Colorants,” Copending Application U.S. Ser. No.10/186,023, filed Jun. 27, 2002, entitled “Dimeric Azo PyridoneColorants,” and Copending Application U.S. Ser. No. 10/184,266, filedJun. 27, 2002, entitled “Phase Change Inks Containing Dimeric AzoPyridone Colorants,” the disclosures of each of which are totallyincorporated herein by reference.

[0223] Other ink colors besides the subtractive primary colors can bedesirable for applications such as postal marking or industrial markingand labeling using phase change printing, and the present invention isapplicable to these needs. Further, infrared (1R) or ultraviolet (UV)absorbing dyes can also be incorporated into the inks of the presentinvention for use in applications such as “invisible” coding or markingof products. Examples of such infrared and ultraviolet absorbing dyesare disclosed in, for example, U.S. Pat. No. 5,378,574, U.S. Pat. No.5,146,087, U.S. Pat. No. 5,145,518, U.S. Pat. No. 5,543,177, U.S. Pat.No. 5,225,900, U.S. Pat. No. 5,301,044, U.S. Pat. No. 5,286,286, U.S.Pat. No. 5,275,647, U.S. Pat. No. 5,208,630, U.S. Pat. No. 5,202,265,U.S. Pat. No. 5,271,764, U.S. Pat. No. 5,256,193, U.S. Pat. No.5,385,803, and U.S. Pat. No. 5,554,480, the disclosures of each of whichare totally incorporated herein by reference.

[0224] The colorant is present in the phase change ink of the presentinvention in any desired or effective amount to obtain the desired coloror hue, in one embodiment at least about 0.1 percent by weight of theink, in another embodiment at least about 0.5 percent by weight of theink, and in yet another embodiment at least about 2 percent by weight ofthe ink, and in one embodiment no more than about 15 percent by weightof the ink, in another embodiment no more than about 10 percent byweight of the ink, in yet another embodiment no more than about 8percent by weight of the ink, and in still another embodiment no morethan about 6 percent by weight of the ink, although the amount can beoutside of these ranges.

[0225] The inks of the present invention can also optionally contain anantioxidant. The optional antioxidants of the ink compositions protectthe images from oxidation and also protect the ink components fromoxidation during the heating portion of the ink preparation process.Specific examples of suitable antioxidants include NAUGUARD® 524,NAUGUARD® 76, and NAUGUARD® 512, commercially available from UniroyalChemical Company, Oxford, Ct., IRGANOX® 1010, commercially availablefrom Ciba Geigy, and the like. When present, the optional antioxidant ispresent in the ink in any desired or effective amount, in one embodimentof at least about 0.01 percent by weight of the ink, in anotherembodiment of at least about 0.1 percent by weight of the ink, and inyet another embodiment of at least about 1 percent by weight of the ink,and in one embodiment of no more than about 20 percent by weight of theink, in another embodiment of no more than about 5 percent by weight ofthe ink, and in yet another embodiment of no more than about 3 percentby weight of the ink, although the amount can be outside of theseranges.

[0226] The inks of the present invention can also optionally contain aviscosity modifier. Examples of suitable viscosity modifiers includealiphatic ketones, such as stearone, and the like. When present, theoptional viscosity modifier is present in the ink in any desired oreffective amount, in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 1 percent byweight of the ink, and in yet another embodiment of at least about 10percent by weight of the ink, and in one embodiment of no more thanabout 99 percent by weight of the ink, in another embodiment of no morethan about 30 percent by weight of the ink, and in yet anotherembodiment of no more than about 15 percent by weight of the ink,although the amount can be outside of these ranges.

[0227] Other optional additives to the inks include clarifiers, such asUNION CAMP® X37-523-235 (commercially available from Union Camp), in anamount in one embodiment of at least about 0.01 percent by weight of theink, in another embodiment of at least about 0.1 percent by weight ofthe ink, and in yet another embodiment of at least about 5 percent byweight of the ink, and in one embodiment of no more than about 98percent by weight of the ink, in another embodiment of no more thanabout 50 percent by weight of the ink, and in yet another embodiment ofno more than about 10 percent by weight of the ink, although the amountcan be outside of these ranges, tackifiers, such as FORAL® 85, aglycerol ester of hydrogenated abietic (rosin) acid (commerciallyavailable from Hercules), FORAL® 105, a pentaerythritol ester ofhydroabietic (rosin) acid (commercially available from Hercules),CELLOLYN® 21, a hydroabietic (rosin) alcohol ester of phthalic acid(commercially available from Hercules), ARAKAWA KE-311 Resin, atriglyceride of hydrogenated abietic (rosin) acid (commerciallyavailable from Arakawa Chemical Industries, Ltd.), synthetic polyterpeneresins such as NEVTAC® 2300, NEVTAC® 100, and NEVTAC® 80 (commerciallyavailable from Neville Chemical Company), WINGTACK® 86, a modifiedsynthetic polyterpene resin (commercially available from Goodyear), andthe like, in an amount in one embodiment of at least about 0.1 percentby weight of the ink, in another embodiment of at least about 5 percentby weight of the ink, and in yet another embodiment of at least about 10percent by weight of the ink, and in one embodiment of no more thanabout 98 percent by weight of the ink, in another embodiment of no morethan about 75 percent by weight of the ink, and in yet anotherembodiment of no more than about 50 percent by weight of the ink,although the amount can be outside of these range, adhesives, such asVERSAMID® 757, 759, or 744 (commercially available from Henkel), in anamount in one embodiment of at least about 0.1 percent by weight of theink, in another embodiment of at least about 1 percent by weight of theink, and in yet another embodiment of at least about 5 percent by weightof the ink, and in one embodiment of no more than about 98 percent byweight of the ink, in another embodiment of no more than about 50percent by weight of the ink, and in yet another embodiment of no morethan about 10 percent by weight of the ink, although the amount can beoutside of these ranges, plasticizers, such as UNIPLEX® 250(commercially available from Uniplex), the phthalate ester plasticizerscommercially available from Monsanto under the trade name SANTICIZER®,such as dioctyl phthalate, diundecyl phthalate, alkylbenzyl phthalate(SANTICIZER® 278), triphenyl phosphate (commercially available fromMonsanto), KP-140®, a tributoxyethyl phosphate (commercially availablefrom FMC Corporation), MORFLEX® 150, a dicyclohexyl phthalate(commercially available from Morflex Chemical Company Inc.), trioctyltrimellitate (commercially available from Eastman Kodak Co.), and thelike, in an amount in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 1 percent byweight of the ink, and in yet another embodiment of at least about 2percent by weight of the ink, and in one embodiment of no more thanabout 50 percent by weight of the ink, in another embodiment of no morethan about 30 percent by weight of the ink, and in yet anotherembodiment of no more than about 10 percent by weight of the ink,although the amount can be outside of these ranges, and the like.

[0228] Optionally, the inks of the present invention contain a componentthat, in its pure form, is a liquid at room temperature (typically about20° C.), but, when incorporated into the inks of the present invention,enable the ink to be a solid at 35° C. or higher. The selected liquid ormixture of liquids are chosen to be compatible with the other inkcomponents, and can be either polar or nonpolar in nature. Specificexamples of suitable liquids include aliphatic hydrocarbons, includingthose with boiling points of about 150° C. or higher, such as squalene,ISOPAR® V, and the like, polar liquids such as glycol ethers, esters,amides, alcohols, and the like, with specific examples including butylcarbitol, tripropylene glycol monomethyl ether, 1-phenoxy-2-propanol,dibutyl phthalate, dibutyl sebacate, 1-dodecanol, and the like, as wellas mixtures thereof.

[0229] The ink compositions of the present invention typically are solidat temperatures of about 35° C. and lower, preferably solid attemperatures of about 50° C. and lower, more preferably solid attemperatures of about 70° C. and lower, and even more preferably solidat temperatures of about 80° C. and lower, and typically have viscosityvalues of from about 5 to 30 centipoise at temperatures no higher thanabout 160° C., preferably no higher than about 140° C., and morepreferably no higher than about 120° C., although the temperature atwhich these viscosities are achieved can be outside of these ranges.

[0230] The ink compositions of the present invention generally haveviscosities at the jetting temperature (typically no lower than about75° C., preferably no lower than about 100° C., and more preferably nolower than about 120° C., and typically no higher than about 180° C.,preferably no higher than about 150° C., and more preferably no higherthan about 130° C., although the jetting temperature can be outside ofthese ranges) typically of no more than about 30 centipoise, preferablyno more than about 20 centipoise, and even more preferably no more thanabout 15 centipoise, and typically of no less than about 2 centipoise,preferably no less than about 5 centipoise, and even more preferably noless than about 7 centipoise, although the melt viscosity can be outsideof these ranges.

[0231] The ink compositions of the present invention can be prepared byany desired or suitable method. For example, the ink ingredients can bemixed together, followed by heating, typically to a temperature of fromabout 100 to about 140° C., although the temperature can be outside ofthis range, and stirring or milling until a homogeneous ink compositionis obtained, followed by cooling the ink to ambient temperature(typically, from about 20 to about 25° C.). The inks of the presentinvention are solid at ambient temperature.

[0232] The present invention is also directed to a process which entailsincorporating an ink of the present invention into an ink jet printingapparatus, melting the ink, and causing droplets of the melted ink to beejected in an imagewise pattern onto a recording sheet. In one specificembodiment, the printing apparatus employs a piezoelectric printingprocess wherein droplets of the ink are caused to be ejected inimagewise pattern by oscillations of piezoelectric vibrating elements.In another specific embodiment, the droplets of melted ink are caused tobe ejected onto an intermediate transfer member, followed by transfer ofthe image from the intermediate transfer member to a recording sheet. Ina specific embodiment, the intermediate transfer member is heated to atemperature above that of the final recording sheet and below that ofthe melted ink in the printing apparatus. Inks of the present inventioncan also be employed in other hot melt printing processes, such as hotmelt thermal ink jet printing, hot melt continuous stream or deflectionink jet printing, hot melt acoustic ink jet printing, or the like.

[0233] Any suitable substrate or recording sheet can be employed,including plain papers such as Xerox® 4024 papers, Xerox® Image Seriespapers, Courtland 4024 DP paper, ruled notebook paper, bond paper,silica coated papers such as Sharp Company silica coated paper, JuJopaper, and the like, transparency materials, fabrics, textile products,plastics, polymeric films, inorganic substrates such as metals and wood,and the like. In a preferred embodiment, the process entails printingonto a porous or ink absorbent substrate, such as plain paper.

[0234] Specific embodiments of the invention will now be described indetail. These examples are intended to be illustrative, and theinvention is not limited to the materials, conditions, or processparameters set forth in these embodiments. All parts and percentages areby weight unless otherwise indicated.

EXAMPLE I Synthesis of1,3-Bis(4-[N-(2,4-bis(N-octylamino)-1,3,5-triazin-6-yl)amino]phenoxy)-2,2-bis[(4-[N-(2,4-bis(N-octylamino)-1,3,5-triazin-6-yl)amino]phenoxy)methyl]propanePart A

[0235] Pentaerythritol tetratosylate was prepared as follows:

[0236] A mixture of pentaerythritol (27.20 grams, 199.8 mmol; obtainedfrom Aldrich Chemical Co., Milwaukee, Wis.) and p-toluenesulfonylchloride (171.0 grams, 897.0 mmol; obtained from Aldrich Chemical Co.,Milwaukee, Wis.) in dry pyridine (300 milliliters; obtained fromAnachemia) was stirred for 48 hours under nitrogen gas. This mixture wasthen added to 2 liters of 6 Normal hydrochloric acid. The resultingwhite precipitate was filtered and washed with methanol. The solid wasrecrystallized from benzene to afford pure pentaerythritol tetratosylate(136.5 grams, 181.3 mmol, 91 percent yield) as white crystals: mp155-156° C.; IR (KBr) 3047, 2958, 2926, 1907, 1599, 1468, 1367, 1296,1174, 1180, 1096, 976, 835, 666, 607, 554 cm⁻¹; ¹H NMR (400 MHz, CDCl₃)δ 7.68 (d, 8H, 3J=8.2 Hz), 7.36 (d, 8H, ³J=8.2 Hz), 3.82 (s, 8H), 2.47(s, 12H); ¹³C NMR (100 MHz, CDCl₃) δ 145.86, 131.50, 130.38, 128.15,65.74, 43.41, 21.90; MS (FAB, 3-nitrobenzyl alcohol) m/e 753; Anal.Calcd for C₃₃H₃₆O₁₂S₄: C, 52.64; H, 4.82; S, 17.04. Found: C, 52.98; H,4.77; S, 17.60.

Part B

[0237] 1,3-Bis(4-nitrophenoxy)-2,2-bis[(4-nitrophenoxy)methyl]propanewas prepared as follows:

[0238] A mixture of pentaerythritol tetratosylate (48.05 grams, 63.82mmol, prepared as described in Part A of this Example) and 4-nitrophenolsodium salt (51.4 grams, 319.1 mmol; obtained from Aldrich Chemical Co.)in absolute ethanol (500 milliliters) was heated at 170° C. in a Parrreactor for 20 hours. The mixture was then cooled to room temperatureand filtered. The resulting crude solid was washed with water until theyellow color disappeared and then with methanol. The residue wasrecrystallized from DMSO to afford pure1,3-bis(4-nitrophenoxy)-2,2-bis[(4-nitrophenoxy)methyl]propane (28.26grams, 45.54 mmol, 71 percent yield) as small light brown crystals: mp274-282° C.; IR (KBr) 3108, 3080, 2959, 1608, 1592, 1514, 1461, 1343,1251, 1174, 1111, 1050, 1032, 852, 755, 690 cm⁻¹; ¹H NMR (400 MHz,DMSO-d₆, 373° K.) δ 8.14 (d, 8H, ³J=8.8 Hz), 7.19 (d, 8H, 3J=8.8 Hz),4.54 (s, 8H); ¹³C NMR (100 MHz, DMSO-d₆, 373° K.) δ 162.89, 141.17,124.75, 114.78, 67.14, 44.38; MS (FAB, 3-nitrobenzyl alcohol) m/e 621.1;Anal. Calcd for C₂₉H₂₄N₄O₁₂: C, 56.13; H, 3.90; N, 9.03. Found: C,55.98; H, 3.81; N, 8.98.

Part C

[0239] 1,3-Bis(4-aminophenoxy)-2,2-bis [(4-aminophenoxy) methyl]propanewas prepared as follows:

[0240] A mixture of1,3-bis(4-nitrophenoxy)-2,2-bis[(4-nitrophenoxy)methyl]propane (15.43grams, 24.87 mmol; prepared as described in Part B of this Example) andPd/C 10% (1.58 grams, obtained from Aldrich Chemical Co.) was stirredfor 70 hours in tetrahydrofuran (400 milliliters) under 180 pounds persquare inch of hydrogen gas. The mixture was then filtered over CELITE;and the solvent was removed by evaporation under reduced pressure. Theresidue was recrystallized from nitrobenzene/benzene to afford pure1,3-bis(4-aminophenoxy)-2,2-bis [(4-aminophenoxy)methyl]propane (11.17grams, 22.31 mmol, 90 percent yield) as small light brown crystals: mp210-211° C.; IR (KBr) 3434, 3351, 3050, 2932, 1625, 1511, 1467, 1232,1041, 1172, 831, 523 cm⁻¹; ¹H NMR (400 MHz, DMSO-d₆) δ 6.66 (d, 8H,3J=8.4 Hz), 6.47 (d, 8H, 3J=8.4 Hz), 4.62 (s, 8H), 4.03 (s, 8H); ¹³C NMR(100 MHz, DMSO-d₆) δ 150.14, 142.73, 115.76, 114.86, 67.06, 44.59; MS(FAB, 3-nitrobenzyl alcohol) m/e 500.3; Anal. Calcd for C₃₃H₂₄N₄O₄: C,69.58; H, 6.44; N, 11.19. Found: C, 69.33; H, 6.78; N, 10.91.

Part D

[0241]1,3-Bis(4-[N-(2,4-dichloro-1,3,5-triazin-6-yl)amino]phenoxy)-2,2-bis[(4-[N-(2,4-dichloro-1,3,5-triazin-6-yl)amino]phenoxy)methyl]propane wasprepared as follows:

[0242] A solution of1,3-bis(4-aminophenoxy)-2,2-bis[(4-aminophenoxy)methyl]propane (5.00grams, 10.0 mmol; prepared as described in Part C of this Example) in120 milliliters of a mixture of dry acetone and tetrahydrofuran (1:1(v/v)) was added dropwise to a solution of cyanuric chloride (7.75grams, 42.0 mmol; obtained from Aldrich Chemical Co.) in 200 millilitersof dry acetone at −10° C. This mixture was stirred for 1 hour at −10° C.and was then added, with Na₂CO₃ (4.45 grams, 42.0 mmol), to 1.5 litersof cold water to give a precipitate. The white solid was filtered off,dried, and dissolved in dichloromethane to remove insoluble material(hydrolyzed product). The resulting solution was filtered over CELITEand dried with magnesium sulfate. Volatiles were removed under reducedpressure, and the residue was dried under vacuum to afford pure1,3-bis(4-[N-(2,4-dichloro-1,3,5-triazin-6-yl)amino]phenoxy)-2,2-bis[(4-[N-(2,4-dichloro-1,3,5-triazin-6-yl)amino]phenoxy)methyl]propane(9.20 grams, 8.42 mmol, 84 percent yield) as a white solid: softeningpoint 143-145° C.; mp 240-250° C.; IR (KBr) 3366, 3268, 3123, 2947,1609, 1550, 1506, 1386, 1318, 1219, 1167, 1019, 846, 829, 794 cm⁻¹; ¹HNMR (400 MHz, CDCl₃) δ 7.47 (s, 4H), 7.40 (d, 8H, 3J=9.0 Hz), 6.96 (d,8H, 3J=9.0 Hz), 4.36 (s, 8H); ¹³C NMR (100 MHz, CDCl₃) δ 171.46, 164.44,156.93, 129.12, 123.93, 115.39, 66.90, 45.11; MS (FAB, 3-nitrobenzylalcohol) m/e 1092.7; Anal. Calcd for C₄₁H₂₈C₁₈N₁₆O₄: C, 45.08; H, 2.58;N, 20.52. Found: C, 45.07; H, 2.58; N, 20.12.

[0243] The hydrolysis products are insoluble in dichloromethane.Purification can be done by filtration over silica gel with 35 percentethyl acetate/hexane, but the loss of at least 50 percent of the productmay occur. Excess cyanuric chloride can be removed from the mixture bytriturating with diethyl ether.

Part E

[0244]1,3-Bis(4-[N-(2,4-bis(N-octylamino)-1,3,5-triazin-6-yl)amino]phenoxy)-2,2-bis[(4-[N-(2,4-bis(N-octylamino)—1,3,5-triazin-6-yl)amino]phenoxy)methyl]propanewas prepared as follows:

[0245] A mixture of1,3-bis(4-[N-(2,4-dichloro-1,3,5-triazin-6-yl)amino]phenoxy)-2,2-bis[(4-[N-(2,4-dichloro-1,3,5-triazin-6-yl)amino]phenoxy)methyl]propane(3.88 grams, 3.55 mmol; prepared as described in Part D of this Example)and octylamine (11.7 milliliters, 71.0 mmol; obtained from AldrichChemical Co.) in dioxane (30 milliliters) was heated at reflux for 3hours. The mixture was then cooled and added to 400 milliliters of asolution of 1 Normal NaOH and methanol (1:1 (v/v)). The resulting whitesolid was filtered off and dissolved in tetrahydrofuran. This solutionwas filtered over silica gel, and the volatiles were removed underreduced pressure. The residue was triturated in methanol and then driedunder vacuum to afford pure1,3-bis(4-[N-(2,4-bis(N-octylamino)-1,3,5-triazin-6-yl)amino]phenoxy)-2,2-bis[(4-[N-(2,4-bis(N-octylamino)-1,3,5-triazin-6-yl)amino]phenoxy)methyl]propane(4.50 grams, 2.45 mmol, 69 percent yield) as white powder: softeningpoint 94-96° C.; IR (KBr) 3434, 3274, 2925, 2854, 1579, 1506, 1421,1367, 1226, 1030, 810 cm⁻¹; ¹H NMR (400 MHz, DMSO-d₆, 373° K.) δ 8.11(s, 4H), 7.60 (d, 8H, ³J=8.9 Hz), 6.84 (d, 8H, 3J=8.9 Hz), 6.12 (s, 8H),4.25 (s, 8H), 3.26 (td, 16H, ³J_(t)=6.6 Hz, ³J_(d)=6.6 Hz), 1.53 (m,16H), 1.29 (m, 80H), 0.86 (t, 24H, 3J=7.1 Hz); ¹³C NMR (100 MHz,DMSO-d₆, 373° K.) δ 165.54, 163.77, 153.31, 133.96, 120.76, 114.27,67.15, 44.47, 39.61, 30.56, 28.87, 28.14, 27.96, 25.90, 21.29, 13.00; MS(FAB, 3-nitrobenzyl alcohol) m/e 1834.6; Anal. Calcd for C₁₀₅H₁₇₂N₂₄O₄:C, 68.74; H, 9.45; N, 18.32. Found: C, 68.31; H, 9.58; N, 18.34.

[0246] Sometimes the precipitation step gives a gum as the product. Thisgum can be dried under vacuum to obtain a solid product.

[0247] Purification can be done if desired by chromatography on silicagel using chloroform as eluant.

Part F

[0248] The methods used to prepare the compound of the formula

[0249] were also used to prepare compounds of the formula

EXAMPLE II

[0250] The process of Example I is repeated except that in Part E, thecompound of the formula

[0251] is partially hydrolyzed prior to reaction with octylamine.Partial hydrolysis is carried out by exposure to water or air to resultin compounds in which variable numbers of chloride groups are replacedby hydroxy groups. One example of such a compound is of the formula

[0252] When the partially hydrolyzed compound is subsequently reactedwith octylamine, the resulting compound is of the formula

EXAMPLE III Synthesis ofTetrakis[(4-[N-[4,6-bis(N-octylamino)-1,3,5-triazin-2-yl]amino]phenoxy)methyl]methane

[0253]

[0254] A solution of cyanuric chloride (36.9 grams, 200 mmol; obtainedfrom Aldrich Chemical Co., Milwaukee, Wis.) in 100 milliliters of drytetrahydrofuran was added dropwise to a solution of1,3-bis(4-aminophenoxy)-2,2-bis[(4-aminophenoxy)methyl]propane (25grams, 50.0 mmol, prepared as described in Part C of Example I) in 500milliliters of dry tetrahydrofuran at −78° C. The mixture was stirredand allowed to warm up to room temperature for 2 hours. Octylamine (165milliliters, 1.00 mol; obtained from Aldrich Chemical Co.) was thenadded and the mixture was stirred at reflux for 3 hours. The mixture wassubsequently cooled to room temperature, water was added, and a gummyprecipitate (like glue) was filtered. The precipitate was dissolved inhot dimethylformamide, ethanol was added (3 liters), and trituration wasdone until the product became a fine solid. The solid was then filtered,washed with methanol, and dried for 2 days under reduced pressure toaffordtetrakis[(4-[N-[4,6-bis(N-octylamino)-1,3,5-triazin-2-yl]amino]phenoxy)methyl]methane(65.0 grams, 35.4 mmol, 70 percent yield) as a white solid: softeningpoint 94-96° C.; IR (KBr) 3434, 3274, 2925, 2854, 1579, 1506, 1421,1367, 1226, 1030, 810 cm⁻¹; ¹H NMR (400 MHz, DMSO-d₆, 373° K.) δ 8.11(s, 4H), 7.60 (d, 8H, ³J=8.9 Hz), 6.84 (d, 8H, 3J=8.9 Hz), 6.12 (s, 8H),4.25 (s, 8H), 3.26 (td, 16H, ³J_(t)=6.6 Hz, ³J_(d)=6.6 Hz), 1.53 (m,16H), 1.29 (m, 80H), 0.86 (t, 24H, 3J=7.1 Hz); ¹³C NMR (100 MHz,DMSO-d₆, 373° K.) δ 165.54, 163.77, 153.31, 133.96, 120.76, 114.27,67.15, 44.47, 39.61, 30.56, 28.87, 28.14, 27.96, 25.90, 21.29, 13.00; MS(FAB, 3-nitrobenzyl alcohol) m/e 1834.6; Anal. Calcd for C₁₀₅H₁₇₂N₂₄O₄:C, 68.74; H, 9.45; N, 18.32. Found: C, 68.31; H, 9.58; N, 18.34.

[0255] Purification can be done if desired by chromatography on silicagel using chloroform as eluant.

[0256] The same protocol can be used to make similar derivatives ofother compounds in which multiple amino groups are attached to a varietyof central cores. In all cases, the intermediate aminodichlorotriazines,obtained after addition of cyanuric chloride, can be treated with avariety of primary and secondary alkylamines to give rise to compoundswith different alkyl substituents.

EXAMPLE IV

[0257] The process of Example III is repeated except that butylamine isused instead of octylamine. The resulting product is of the formula

EXAMPLE V

[0258] The process of Example III is repeated except that hexylamine isused instead of octylamine. The resulting product is of the formula

EXAMPLE VI

[0259] The process of Example III is repeated except that decylamine isused instead of octylamine. The resulting product is of the formula

EXAMPLE VII

[0260] The process of Example III is repeated except that octadecylamineis used instead of octylamine. The resulting product is of the formula

EXAMPLE VIII

[0261] A compound of the formula

[0262] was prepared as follows.

Part A

[0263] 1,5-Bis(4-nitrophenoxy)pentane was prepared as follows:

[0264] A mixture of 1,5-dibromopentane (16.0 milliliters; 118 mmol;obtained from Aldrich Chemical Co., Milwaukee, Wis.) and 4-nitrophenolsodium salt (45.7 grams; 284 mmol; obtained from Aldrich Chemical Co.)in dimethylformamide (100 milliliters) was heated at 150° C. for 20hours. The mixture was then cooled to room temperature and water (200milliliters) was added. The resulting precipitate was filtered, washedwith water, and recrystallized from ethanol to afford pure1,5-bis(4-nitrophenoxy)pentane (33.1 grams, 95.5 mmol, 80 percent yield)as small light-yellow crystals: mp 101-102° C.; IR (KBr) 3113, 2939,1591, 1497, 1453, 1329, 1266, 1240, 1175, 1107, 1045, 999, 929, 847,751, 654 cm⁻¹; ¹H NMR (100 MHz, CDCl₃) δ 8.19 (d, 4H, 3J=9.2 Hz), 6.95(d, 4H, ³J=9.2 Hz), 4.10 (t, 4H, 3J=6.2 Hz), 1.93 (q, 4H, ³J=6.8 Hz),1.62 (q, 2H, 3J=6.8 Hz); ¹³C NMR (75 MHz, CDCl₃) δ 164.24, 141.58,126.10, 114.56, 68.70, 28.87, 22.79; MS (FAB, 3-nitrobenzyl alcohol) m/e346.2; Anal. Calcd for C₁₇H₁₈N₂O₆: C, 58.96; H, 5.24; N, 8.09. Found: C,58.69; H, 5.45; N, 8.07.

Part B

[0265] 1,5-Bis(4-aminophenoxy)pentane was prepared as follows:

[0266] A mixture of 1,5-bis(4-nitrophenoxy)pentane (32.7 grams, 94.4mmol; prepared as described in Part A of this Example) and Pd/C 10%(1.00 gram, obtained from Aldrich Chemical Co.) was stirred for 20 hoursin tetrahydrofuran (400 milliliters) under 200 pounds per square inch ofhydrogen gas. The mixture was then filtered over CELITE, and the solventwas removed by evaporation under reduced pressure. The resulting crudesolid was recrystallized from ethanol to afford pure1,5-bis(4-aminophenoxy)pentane (24.4 grams, 85.1 mmol, 90 percent yield)as small colorless crystals: mp 78-79° C.; IR (KBr) 3433, 3353, 3217,2949, 2868, 1856, 1632, 1511, 1473, 1396, 1228, 1031, 1002, 825, 517cm⁻¹; ¹H NMR (300 MHz, CDCl₃) δ 6.76 (d, 4H, 3J=8.8 Hz), 6.64 (d, 4H,3J=8.8 Hz), 3.92 (td, 4H, 3J=6.4 Hz, 4J=1.4 Hz), 3.40 (s, 4H), 1.82 (q,4H, 3J=6.8 Hz), 1.62 (q, 2H, 3J=6.8 Hz); ¹³C NMR (75 MHz, CDCl₃) δ151.31, 140.06, 116.51, 115.78, 68.58, 29.32, 22.83; MS (FAB,3-nitrobenzyl alcohol) m/e 286.7; Anal. Calcd for C₁₇H₂₂N₂O₂: C, 71.30;H, 7.74; N, 9.78. Found: C, 71.11; H, 8.22; N, 9.85.

[0267] This procedure can also be used to reduce related derivativeswith variable alkyl chains. For example, the procedure can be used toreduce 1,3-bis(4-nitrophenoxy)-2,2-bis[(4-nitrophenoxy)methyl]propane.

Part C

[0268] N,N″-[1,5-Pentanediylbis(oxy-4,1-phenylene)]bis[N′-octyl]urea wasprepared as follows:

[0269] A solution of triphosgene (2.76 grams, 9.31 mmol; obtained fromAldrich Chemical Co., Milwaukee, Wis.) in 20 milliliters of drytetrahydrofuran was added dropwise to a solution of1,5-bis(4-aminophenoxy)pentane (4.00 grams, 14.0 mmol; prepared asdescribed in Part B of this Example) and triethylamine (7.78milliliters, 55.9 mmol; obtained from Anachemia, Rouses Point, N.Y.) in150 milliliters of dry tetrahydrofuran at −78° C. The mixture wasstirred and allowed to warm up to room temperature for 1 hour.Octylamine (10.2 milliliters, 61.5 mmol, obtained from Aldrich ChemicalCo.) was then added and the mixture was stirred at 50° C. for 15minutes. The mixture was subsequently cooled to room temperature andwater (300 milliliters) was added. The resulting precipitate wasfiltered and recrystallized from dimethylformamide to afford pureN,N″-[1,5-pentanediylbis(oxy-4,1-phenylene)]bis[N′-octyl]urea (5.23grams, 8.76 mmol, 63 percent yield) as a colorless solid. mp 185-186°C.; IR (KBr) 3344, 3304, 2927, 2853, 1635, 1564, 1511, 1478, 1294, 1234,1034, 828, 648, 530 cm⁻¹; ¹H NMR (400 MHz, DMSO-d₆) 68.14 (s, 2H), 7.24(d, 4H, 3J=8.8 Hz), 6.78 (d, 4H, 3J=8.8 Hz), 5.97 (s, 2H), 3.89 (t, 4H,³J=8.8 Hz), 3.03 (m, 4H), 1.76 (q, 4H, 3J=6.8 Hz), 1.53 (q, 2H, 3J=6.8Hz), 1.39 (m, 4H), 1.25 (m, 20H), 0.85 (t, 6H, 3J=7.1 Hz); Anal. Calcdfor C₃₅H₅₆N₄O₄: C, 70.43; H, 9.46; N, 9.39. Found: C, 70.38; H, 10.01;N, 9.47.

Part D

[0270] This procedure can also be used with a variety of compounds withmultiple amino groups joined to diverse central cores. For example, itwas used to convert1,3-bis(4-aminophenoxy)-2,2-bis[(4-aminophenoxy)methyl]propane to acompound of the formula

[0271] by the method described hereinabove.

EXAMPLE IX

[0272] The procedure of Example VIII is repeated except that in Part A,1,1-dibromomethane is used instead of 1,5-dibromopentane. The finalproduct after Part C is of the formula

EXAMPLE X

[0273] The procedure of Example VIII is repeated except that in Part A,1,3-dibromopropane is used instead of 1,5-dibromopentane. The finalproduct after Part C is of the formula

EXAMPLE XI

[0274] The procedure of Example VIII is repeated except that in Part A,1,7-dibromoheptane is used instead of 1,5-dibromopentane. The finalproduct after Part C is of the formula

EXAMPLE XII

[0275] The procedure of Example VIII is repeated except that in Part A,1,9-dibromononane is used instead of 1,5-dibromopentane. The finalproduct after Part C is of the formula

EXAMPLE XIII Synthesis of1,5-bis[4-[N-[4,6-bis(N-octylamino)-1,3,5-triazin-2-yl]amino]phenoxy]pentane

[0276]

[0277] A solution of cyanuric chloride (6.44 grams, 34.9 mmol; obtainedfrom Aldrich Chemical Co.) in dry tetrahydrofuran (50 milliliters) wasadded dropwise to a solution of 1,5-bis(4-aminophenoxy)pentane (5.00grams, 17.46 mmol; prepared as described in Part B of Example VIII) indry tetrahydrofuran (100 milliliters) at −78° C. The mixture was stirredand allowed to warm up to room temperature for 2 hours. Octylamine (23.0milliliters, 139 mmol; obtained from Aldrich Chemical Co.) was thenadded and the mixture was stirred at reflux for 3 hours. The mixture wascooled to room temperature, water was added, and the resulting gummyprecipitate (like glue) was filtered. The precipitate was dissolved inchloroform and filtered over silica gel. The volatiles were removedunder reduced pressure to afford1,5-Bis[4-[N-[4,6-bis(N-octylamino)-1,3,5-triazin-2-yl]amino]phenoxy]pentane(7.51 grams, 7.88 mmol, 45 percent yield) as a white solid: IR (KBr)3410, 3279, 2926, 2855, 1575, 1506, 1423, 1369, 1230, 1031,810 cm⁻¹.

EXAMPLE XIV Synthesis ofTetrakis[(4-[N-[4-amino-6-(N-hexylamino)-1,3,5-triazin-2-yl]amino]phenoxy)methyl]methane(also Called1,3-Bis(4-[N-[2-amino-4-(N-octylamino)-1,3,5-triazin-6-yl)amino]phenoxy)-2,2-bis[(4-[N-[2-amino-4-(N-octylamino)-1,3,5-triazin-6-yl)amino]phenoxy)methyl]propane)

[0278]

[0279] Ammonium hydroxide (30 percent in water, 21.0 milliliters, 160mmol) was added to a solution oftetrakis[(4-[N-(2,4-dichloro-1,3,5-triazin-6-yl)amino]phenoxy)methyl]methane(6.20 grams, 5.68 mmol; prepared as described in Part D of Example I) intetrahydrofuran (200 milliliters) at −10° C. This mixture was stirredand warmed up to room temperature for 2 hours. Thereafter, the volatileswere removed under reduced pressure and a solution of methanol/water(300 milliliters, 1:1, v/v) was added. This mixture was triturated for30 minutes and filtered. The crude solid was then dissolved in dioxane(60 milliliters), hexylamine (7.50 milliliters, 56.8 mmol) was added,and the mixture was heated at reflux for 3 hours. The mixture was thencooled to room temperature and water was added. The resulting solid wasfiltered, washed with methanol, and dried for 2 days under reducedpressure to affordtetrakis[(4-[N-[4,6-bis(N-octylamino)-1,3,5-triazin-2-yl]amino]phenoxy)methyl]methane(7.09 grams, 5.57 mmol, 98 percent yield) as a white solid. The solidwas dissolved in tetrahydrofuran and filtered over silica gel to affordpuretetrakis[(4-[N-[4,6-bis(N-octylamino)-1,3,5-triazin-2-yl]amino]phenoxy)methyl]methane(3.31 grams, 2.16 mmol, 38 percent yield): mp 131-133° C.; IR (KBr)3405, 3313, 3176, 2927, 2855, 1589, 1525, 1455, 1418, 1360, 1231, 1031,811 cm⁻¹; ¹H NMR (400 MHz, DMSO-d₆, 373° K.) δ 8.16 (s, 4H), 7.59 (d,8H, 3J=8.8 Hz), 6.86 (d, 8H, 3J=8.8 Hz), 6.17 (s, 4H), 5.73 (s, 8H),4.26 (s, 8H), 3.26 (dt, 8H, ³J_(d)=6.7 Hz, ³J_(t)=6.7 Hz), 1.53 (m, 8H),1.30 (m, 24H), 0.87 (t, 12H, 3J=7.2 Hz); ¹³C NMR (100 MHz, DMSO-d₆, 373°K.) δ 166.56, 165.92, 164.19, 153.43, 133.82, 120.96, 114.35, 67.19,44.48, 39.61, 30.42, 28.78, 25.50, 21.33, 13.00; MS (FAB, 3-nitrobenzylalcohol) m/e 1273.8; Anal. Calcd for C₆₅H₉₂N₂₄O₄: C, 61.30; H, 7.28; N,26.39. Found: C, 61.41; H, 7.49; N, 26.18. Filtration over silica gel isbelieved to be responsible for the low yield.

[0280] This method can also be used to obtain derivatives in which thetriaminotriazine groups bear substituents with different alkyl groups bysequential introduction of different alkylamines.

EXAMPLE XV

[0281] The procedure of Example XIV is repeated except that butylamineis substituted for hexylamine. The resulting product is of the formula

EXAMPLE XVI

[0282] The procedure of Example XIV is repeated except that octylamineis substituted for hexylamine. The resulting product is of the formula

EXAMPLE XVII

[0283] The procedure of Example XIV is repeated except that decylamineis substituted for hexylamine. The resulting product is of the formula

EXAMPLE XVIII Synthesis of1,1-Bis[4-[N,N-bis[4,6-diamino-1,3,5-triazin-2-yl]amino]phenoxy]methane

[0284]

[0285] Cyanuric chloride (11.473 grams, 62.2 mmol) in drytetrahydrofuran (50 milliliters) was added to a solution of1,1-bis(4-aminophenoxy)methane (3.58 grams, 15.55 mmol; prepared asdescribed in Part B of Example VIII except that 1,1-dibromomethane wasused instead of 1,5-dibromopentane) in dry tetrahydrofuran (175milliliters) at −10° C. The mixture was stirred for 10 minutes andsodium hydride (3.75 grams, 93.3 mmol) was added dropwise. The mixturewas then heated to 60° C. for 16 hours and subsequently filtered onCELITE. The volatiles were removed under reduced pressure and the crudesolid was purified on silica gel using a mixture of AcOEt/hexane (3:7,v/v) as eluant to afford pure1,1-bis[4-[N,N-bis[4,6-dichloro-1,3,5-triazin-2-yl]amino]phenoxy]methane(2.10 grams, 2.55 mmol, 16 percent yield) as a white solid.Chromatography with silica gel is believed to be responsible for the lowyield.

[0286] Ammonium hydroxide (30 percent in water, 20 milliliters) wasadded to a solution of1,1-bis[4-[N,N-bis[4,6-dichloro-1,3,5-triazin-2-yl]amino]phenoxy]methane(1.893 grams, 2.30 mmol, prepared as described in Part A of thisExample) in dry tetrahydrofuran (20 milliliters) in a sealed tube. Themixture was heated to 60° C. for 6 hours and then the volatiles wereremoved under reduced pressure. The resulting solid was washed withwater and with cold methanol to afford1,1-bis[4-[N,N-bis[4,6-diamino-1,3,5-triazin-2-yl]amino] phenoxy]methane (1.50 grams, 2.25 mmol, 98 percent yield) as a white solid:mp>300° C.; IR (KBr) 3330, 3193, 2924, 1626, 1533, 1505, 1450, 1417,1348, 1203, 1003, 815, 791, 622 cm⁻¹; ¹H NMR (400 MHz, DMSO-d₆,) δ 7.02(s, 8H), 6.54 (bs, 16H), 5.82 (s, 2H); ¹³C NMR (100 MHz, DMSO-d_(6,)) δ168.54, 167.96, 153.70, 137.03, 128.50, 116.23, 89.92.

[0287] The sequential addition of 4 equivalents of alkylamine followedby ammonium hydroxide can give access to analogous compounds such as

[0288] An average yield of 70 percent is expected for this process.

EXAMPLE XIX

[0289] Colorless ink compositions containing the materials prepared inExample I (Part E), Example VIII (Part C), Example VIII (Part D),Example XIV, and Example I (Part F) and, for comparison purposes, an inkthat did not contain any of these additives were prepared as follows.

[0290] Ink A: In a stainless steel beaker were combined (1) polyethylenewax (PE 655, obtained from Baker Petrolite, Tulsa, Okla., of the formulaCH₃(CH₂)₅₀CH₃), (2) stearyl stearamide wax (KEMAMIDE® S-180, obtainedfrom Crompton Corporation, Greenwich, Conn.), (3) a tetra-amide resinobtained from the reaction of one equivalent of dimer acid with twoequivalents of ethylene diamine and UNICID® 700 (obtained from BakerPetrolite, Tulsa, Okla., a carboxylic acid derivative of a long chainalcohol), prepared as described in Example 1 of U.S. Pat. No. 6,174,937,the disclosure of which is totally incorporated herein by reference, (4)a urethane resin obtained from the reaction of two equivalents ofABITOL® E hydroabietyl alcohol (obtained from Hercules Inc., Wilmington,Del.), and one equivalent of isophorone diisocyanate, prepared asdescribed in Example 1 of U.S. Pat. No. 5,782,966, the disclosure ofwhich is totally incorporated herein by reference, (5) a urethane resinthat was the adduct of three equivalents of stearyl isocyanate and aglycerol-based alcohol prepared as described in Example 4 of U.S. Pat.No. 6,309,453, the disclosure of which is totally incorporated herein byreference, and (6) NAUGUARD® 445 antioxidant (obtained from UniroyalChemical Co., Middlebury, Conn.). The materials were melted together ata temperature of about 135° C. in an oven, then blended by stirring in atemperature controlled mantle at about 135° C. for about 0.2 hour. Tothis mixture was then added (6) the material prepared in Example I (PartE). After stirring for about 2 additional hours, the ink thus formed wasfiltered through a heated MOTT® apparatus (obtained from MottMetallurgical) using NAE 0.2 micro filter and Whatman #3 filter paper(on top of NAE filter) under a pressure of about 15 pounds per squareinch. The filtered phase change ink was poured into an aluminum mold andallowed to solidify to form an ink block. The colorless phase change inkthus prepared exhibited a viscosity of about 13.4 centipoise as measuredby a Rheometrics cone-plate viscometer at about 140° C., melting pointsof about 86° C. and 104° C. as measured by differential scanningcalorimetry using a DSC 7 from Perkin Elmer, and a glass transitiontemperature (T_(g)) of about 14° C.

[0291] Ink B: Ink B was prepared in a similar manner to that used toprepare Ink A but using the material prepared in Example VIII (Part C)instead of the material prepared in Example I (Part E).

[0292] Ink C: Ink C was prepared in a similar manner to that used toprepare Ink A but using the material prepared in Example VIII (Part D)instead of the material prepared in Example I (Part E).

[0293] Ink D: Ink D was prepared in a similar manner to that used toprepare Ink A but using the material prepared in Example XIV instead ofthe material prepared in Example I (Part E).

[0294] Ink E: Ink E was prepared in a similar manner to that used toprepare Ink A but using the material prepared in Example I (Part F)instead of the material prepared in Example I (Part E).

[0295] Ink F: Ink F was prepared in a similar manner to that used toprepare Ink A but no additive was present.

[0296] Relative amounts of the ingredients in each of these inks,expressed in percent by weight of the ink, are indicated in the tablebelow: Ingredient Ink A Ink B Ink C Ink D Ink E Ink F POLYWAX 34.6434.64 37.36 37.36 34.64 38.30 S-180 19.00 19.00 20.50 20.50 19.00 21.20Tetra-amide 19.22 19.22 20.66 20.66 19.22 21.40 Urethane 10.73 10.7311.53 11.53 10.73 11.96 Resin 1* Urethane 6.23 6.23 6.70 6.70 6.23 6.94Resin 2** Example IE 10.00 — — — — — material Example VIIIC — 10.00 — —— — material Example VIIID — — 3.07 — — — material Example XIV — — —3.07 — — material Example — — — — 10.00 — IF material NAUGUARD 0.18 0.180.18 0.18 0.18 0.20 445 Total 100.0 100.0 100.0 100.0 100.0 100.0

[0297] Rheology and dynamic mechanical analysis data were also obtainedto produce evidence of increased toughness of inks according to thepresent invention. Particularly, the toughness of ink samples wasestimated two ways. In one method, from a plot of tan δ (ratio of lossmodulus, G″, to storage modulus, G′) versus temperature as measured on acontrolled stress rheometer, SR5000 from Rheometrics Scientific, in aconventional parallel plate configuration. The area underneath the tan δversus Temperature curve, between 0° C. and 25° C., is as large orlarger for the inks containing the additives of the present inventioncompared to an ink that does not contain any of these additives. Forexample, Ink A was found to have a toughness value of 1.62 (area undercurve) while ink F had a toughness value of 0.28 under the sameconditions. Similar differences in toughness values are expected forinks B to E compared to ink F. In addition, the toughness as well as theYoung's modulus and flexural strength were estimated by typicalstress-strain measurements at room temperature using a Solid StateAnalyzer, RSAII from Rheometrics Scientific. The samples tested wereprepared as follows: the ink was put into a pan and was melted on ahotplate at 150° C. It was then transferred onto a rectangular mold thatwas sitting on a hot plate at 80 C. The mold was then covered with aflat glass plate and allowed to sit for 10 minutes at 80 C. The samplewas then removed from the mold and allo wed to cool to room temperature.The samples obtained were rectangular, with a length of 49 millimeters,a width of 12 millimeters, and a thickness of 3 millimeters. The dynamicmechanical experiment performed was a dynamic strain rate at 23° C.using a three-point bending geometry configuration. The variation of thestress versus the applied deformation or strain was recorded. The slopefrom the curve stress versus strain is equal to the Young's modulus, thearea under the curve is proportional to the toughness, and the stressvalue at which the sample breaks is the flexural strength. The followingtable summarizes the data for Ink E: Ink E Ink F Young's Modulus 2.72.69 (GPa) Flexural Strength 6.09 4.78 (MPa) Toughness (MPa) 8226 4588

[0298] The values of Young's modulus, flexural strength, and toughnessfor inks A to D compared to those of ink F are also expected to besignificantly improved.

EXAMPLE XX

[0299] Yellow ink compositions containing the materials prepared inExample I (Part E), Example VIII (Part C), Example VIII (Part D),Example XIV, and Example I (Part F) and, for comparison purposes, an inkthat does not contain any of these additives are prepared as follows.

[0300] Ink G: In a stainless steel beaker are combined (1) polyethylenewax (PE 655, obtained from Baker Petrolite, Tulsa, Okla., of the formulaCH₃(CH₂)₅₀CH₃), (2) stearyl stearamide wax (KEMAMIDE® S-180, obtainedfrom Crompton Corporation, Greenwich, Conn.), (3) a tetra-amide resinobtained from the reaction of one equivalent of dimer acid with twoequivalents of ethylene diamine and UNICID® 700 (obtained from BakerPetrolite, Tulsa, Okla., a carboxylic acid derivative of a long chainalcohol), prepared as described in Example 1 of U.S. Pat. No. 6,174,937,the disclosure of which is totally incorporated herein by reference, (4)a urethane resin obtained from the reaction of two equivalents ofABITOL® E hydroabietyl alcohol (obtained from Hercules Inc., Wilmington,Del.), and one equivalent of isophorone diisocyanate, prepared asdescribed in Example 1 of U.S. Pat. No. 5,782,966, the disclosure ofwhich is totally incorporated herein by reference, (5) a urethane resinthat was the adduct of three equivalents of stearyl isocyanate and aglycerol-based alcohol prepared as described in Example 4 of U.S. Pat.No. 6,309,453, the disclosure of which is totally incorporated herein byreference, and (6) NAUGUARD® 445 antioxidant (obtained from UniroyalChemical Co., Middlebury, Conn.). The materials are melted together at atemperature of about 135° C. in an oven, then blended by stirring in atemperature controlled mantle at about 135° C. for about 0.2 hour. Tothis mixture is then added (6) the material prepared in Example I (PartE) and (7) NEOPEN YELLOW 075 (obtained from BASF). After stirring forabout 2 additional hours, the yellow ink thus formed is filtered througha heated MOTTO apparatus (obtained from Mott Metallurgical) using NAE0.2 micro filter and Whatman #3 filter paper (on top of NAE filter)under a pressure of about 15 pounds per square inch. The filtered phasechange ink is poured into an aluminum mold and allowed to solidify toform an ink block. The yellow phase change ink thus prepared exhibits aviscosity of about 13.4 centipoise as measured by a Rheometricscone-plate viscometer at about 140° C., melting points of about 86° C.and 104° C. as measured by differential scanning calorimetry using a DSC7 from Perkin Elmer, a glass transition temperature (T_(g)) of about 14°C., and a spectral strength, determined by using a spectrophotographicprocedure based on the measurement of the colorant in solution bydissolving the solid ink in n-butanol and measuring the absorbance usinga Perkin Elmer Lambda 2S UV/VIS spectrophotometer, of about 3500milliliters absorbance per gram at 429 nanometers.

[0301] Ink H: Ink H is prepared in a similar manner to that used toprepare Ink G but using the material prepared in Example VIII (Part C)instead of the material prepared in Example I (Part E).

[0302] Ink J: Ink J is prepared in a similar manner to that used toprepare Ink G but using the material prepared in Example VIII (Part D)instead of the material prepared in Example I (Part E).

[0303] Ink K: Ink K is prepared in a similar manner to that used toprepare Ink G but using the material prepared in Example XIV instead ofthe material prepared in Example I (Part E).

[0304] Ink L: Ink L is prepared in a similar manner to that used toprepare Ink G but using the material prepared in Example I (Part F)instead of the material prepared in Example I (Part E).

[0305] Ink M: Ink M is prepared in a similar manner to that used toprepare Ink G but no additive such as those prepared in Examples I,VIII, or XIV was present.

[0306] Relative amounts of the ingredients in each of these inks,expressed in percent by weight of the ink, are indicated in the tablebelow: Ingredient Ink G Ink H Ink J Ink K Ink L Ink M POLY WAX 33.9233.92 36.48 36.48 33.92 31.48 S-180 18.59 18.59 19.99 19.99 18.59 20.73Tetra-amide 18.80 18.80 20.21 20.21 18.80 20.95 Urethane 10.49 10.4911.28 11.28 10.49 11.70 Resin 1* Urethane 6.09 6.09 6.55 6.55 6.09 6.79Resin 2** Neopen 2.15 2.15 2.31 2.31 2.15 2.15 Yellow 075 Example IE9.78 — — — — — material Example VIIIC — 9.78 — — — — material ExampleVIIID — — 3.00 — — — material ExampIe XIV — — — 3.00 — — materialExample — — — — 9.78 — IE material NAUGUARD 0.18 0.18 0.18 0.18 0.180.20 445 Total 100.0 100.0 100.0 100.0 100.0 100.0

[0307] The yellow inks thus prepared are printed on HAMMERMILLLASERPRINT® paper (obtained from International Paper, Memphis, Term.) ina XEROX® PHASER 850 printer, which uses a printing process wherein theink is first jetted in an imagewise pattern onto an intermediatetransfer member followed by transfer of the imagewise pattern from theintermediate transfer member to a final recording substrate. Solid fieldimages with a resolution of 355 dpi x 464 dpi are generated from theprinter.

[0308] Another type of printed sample is generated on HAMMERMILLLASERPRINT® paper using K Printing Proofer (manufactured by RK PrintCoat Instrument Ltd., Litlington, Royston, Herts, U.K.). In this method,the tested inks are melted onto a printing plate set at 150° C. A rollerbar fitted with the paper is then rolled over the plate containing themelted ink on its surface. The ink on the paper is cooled, resulting inthree separated images of rectangular blocks. The most intensely coloredblock contains the most ink deposited on the paper, and is thereforeused to obtain scratch value measurements. It is believed that the inksof the present invention will be found to have good scratch resistance.

[0309] Other embodiments and modifications of the present invention mayoccur to those of ordinary skill in the art subsequent to a review ofthe information presented herein; these embodiments and modifications,as well as equivalents thereof, are also included within the scope ofthis invention.

[0310] The recited order of processing elements or sequences, or the useof numbers, letters, or other designations therefor, is not intended tolimit a claimed process to any order except as specified in the claimitself.

What is claimed is:
 1. Compounds of the formulae

wherein Z is a group of the formula —OR₁, a group of the formula —SR₁,or a group of the formula —NR₁R₂, Y is a group of the formula —OR₃, agroup of the formula —SR₃, or a group of the formula —NR₃R₄, n is aninteger representing the number of repeat —(CH₂)— or —(CH₂CH₂O)— units,wherein, provided that at least one of R₁, R₂, R₃, R₄, R₅, and R₆ is ahydrogen atom, provided that at least one of R₁, R₂, R₃, R₄, R₅, and R₆is other than a hydrogen atom, and provided that at least one Z or Ywithin the compound is a group of the formula —NR₁R₂ or a group of theformula —NR₃R₄, R₁, R₂, R₃, R₄, R₅, R₆, and R₇ each, independently ofthe others, is (i) a hydrogen atom, (ii) an alkyl group, (iii) an arylgroup, (iv) an arylalkyl group, or (v) an alkylaryl group, and whereinR₇ can also be (vi) an alkoxy group, (vii) an aryloxy group, (viii) anarylalkyloxy group, (ix) an alkylaryloxy group, (x) a polyalkyleneoxygroup, (xi) a polyaryleneoxy group, (xii) a polyarylalkyleneoxy group,(xiii) a polyalkylaryleneoxy group, (xiv) a silyl group, (xv) a siloxanegroup, (xvi) a polysilylene group, (xvii) a polysiloxane group, or(xviii) a group of the formula

wherein r is an integer representing a number of repeat —CH₂— groups,wherein s is an integer representing a number of repeating —CH₂— groups,and wherein X is (a) a direct bond, (b) an oxygen atom, (c) a sulfuratom, (d) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogen atom,an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (e) a group of the formula —CR₅OR₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and wherein R₆ canalso be


2. Compounds according to claim 1 wherein the compound is of theformulae


3. Compounds according to claim 1 wherein the compound is of theformulae


4. Compounds according to claim 1 wherein Z is a group of the formula—OR₁, a group of the formula —SR₁, or a group of the formula —NR₁R₂, Yis a group of the formula —OR₃, a group of the formula —SR₃, or a groupof the formula —NR₃R₄, n is from 1 to about 100, wherein, provided thatat least one of R₁, R₂, R₃, R₄, R₅, and R₆ is a hydrogen atom, providedthat at least one of R₁, R₂, R₃, R₄, R₅, and R₆ is other than a hydrogenatom, and provided that at least one Z or Y within the compound is agroup of the formula —NR₁R₂ or a group of the formula —NR₃R₄, R₁, R₂,R₃, R₄, R₅, R₆, and R₇ each, independently of the others, is (i) ahydrogen atom, (ii) an alkyl group having at least 1 carbon atom andhaving no more than about 96 carbon atoms, (iii) an aryl group having atleast about 6 carbon atoms and having no more than about 50 carbonatoms, (iv) an arylalkyl group having at least about 7 carbon atoms andhaving no more than about 96 carbon atoms, or (v) an alkylaryl grouphaving at least about 7 carbon atoms and having no more than about 96carbon atoms, and wherein R₇ can also be (vi) an alkoxy group having atleast 1 carbon atom and having no more than about 96 carbon atoms, (vii)an aryloxy group having at least about 6 carbon atoms and having no morethan about 50 carbon atoms, (viii) an arylalkyloxy group having at leastabout 7 carbon atoms and having no more than about 96 carbon atoms, (ix)an alkylaryloxy group having at least about 7 carbon atoms and having nomore than about 96 carbon atoms, (x) a polyalkyleneoxy group wherein thealkyl portion of the repeat alkyleneoxy groups has from about 1 to about12 carbon atoms and wherein the number of repeat alkyleneoxy groups isfrom about 2 to about 50, (xi) a polyaryleneoxy group wherein the arylportion of the repeat aryleneoxy groups has from about 6 to about 14carbon atoms and wherein the number of repeat aryleneoxy groups is fromabout 2 to about 20, (xii) a polyarylalkyleneoxy group wherein thearylalkyl portion of the repeat arylalkyleneoxy groups has from about 7to about 50 carbon atoms and wherein the number of repeatarylalkyleneoxy groups is from about 2 to about 20, (xiii) apolyalkylaryleneoxy group wherein the alkylaryl portion of the repeatalkylaryleneoxy groups has from about 7 to about 50 carbon atoms andwherein the number of repeat alkylaryleneoxy groups is from about 2 toabout 20, (xiv) a silyl group, (xv) a siloxane group, (xvi) apolysilylene group with from 2 to about 100 repeat silylene units,(xvii) a polysiloxane group with from 2 to about 200 repeat siloxaneunits, or (xviii) a group of the formula

wherein r is at least 1, wherein r is no more than about 100, wherein sis at least 1, wherein s is no more than about 100, and wherein X is (a)a direct bond, (b) an oxygen atom, (c) a sulfur atom, (d) a group of theformula —NR₄₀— wherein R₄₀ is a hydrogen atom, an alkyl group with from1 to about 50 carbon atoms, an aryl group with from 6 to about 50 carbonatoms, an arylalkyl group with from about 7 to about 100 carbon atoms,or an alkylaryl group with from about 7 to about 100 carbon atoms, or(e) a group of the formula —CR₅OR₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group with from1 to about 50 carbon atoms, an aryl group with from 6 to about 50 carbonatoms, an arylalkyl group with from about 7 to about 100 carbon atoms,or an alkylaryl group with from about 7 to about 100 carbon atoms, andwherein R₆ can also be


5. Compounds according to claim 1 wherein at least one of R₁, R₂, R₃,R₄, R₅, and R₆ is an unsubstituted alkyl group, an unsubstituted arylgroup, an unsubstituted arylalkyl group, or an unsubstituted alkylarylgroup.
 6. Compounds according to claim 1 wherein at least one of R₁, R₂,R₃, R₄, R₅, and R₆ is a substituted alkyl group, a substituted arylgroup, a substituted arylalkyl group, or a substituted alkylaryl group.7. Compounds according to claim 6 wherein the substituents are hydroxygroups, halogen atoms, amine groups, imine groups, ammonium groups,pyridine groups, pyridinium groups, ether groups, aldehyde groups, estergroups, amide groups, carbonyl groups, thiocarbonyl groups, sulfategroups, sulfonate groups, sulfide groups, sulfoxide groups, phosphinegroups, phosphonium groups, phosphate groups, nitrile groups, mercaptogroups, nitro groups, nitroso groups, sulfone groups, acyl groups, acidanhydride groups, azide groups, azo groups, cyanato groups, isocyanatogroups, thiocyanato groups, isothiocyanato groups, alkoxy groups,aryloxy groups, arylalkyloxy groups, alkylaryloxy groups,polyalkyleneoxy groups wherein the alkyl portion of the repeatalkyleneoxy groups has from about 1 to about 12 carbon atoms and whereinthe number of repeat alkyleneoxy groups is from about 2 to about 50,polyaryleneoxy groups wherein the aryl portion of the repeat aryleneoxygroups has from about 6 to about 14 carbon atoms and wherein the numberof repeat aryleneoxy groups is from about 2 to about 20,polyarylalkyleneoxy groups wherein the arylalkyl portion of the repeatarylalkyleneoxy groups has from about 7 to about 50 carbon atoms andwherein the number of repeat arylalkyleneoxy groups is from about 2 toabout 20, polyalkylaryleneoxy group wherein the alkylaryl portion of therepeat alkylaryleneoxy groups has from about 7 to about 50 carbon atomsand wherein the number of repeat alkylaryleneoxy groups is from about 2to about 20, silyl groups, siloxane groups, polysilylene groups withfrom 2 to about 100 repeat silylene units, polysiloxane groups with from2 to about 200 repeat siloxane units, or mixtures thereof, wherein twoor more substituents can be joined together to form a ring.
 8. Compoundsaccording to claim 1 wherein R₁, R₂, R₃, and R₄ each, independently ofthe others, is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicosyl. 9.Compounds according to claim 1 wherein R₅ is hydrogen.
 10. Compoundsaccording to claim 1 wherein R₆ is hydrogen,


11. Compounds according to claim 1 wherein n is 1, 3, 5, 7, or
 9. 12.Compounds according to claim 1 of the formulae


13. A compound according to claim 1 of the formula


14. A compound according to claim 1 of the formula


15. A compound according to claim 1 of the formula


16. A compound according to claim 1 of the formula


17. A compound according to claim 1 of the formula


18. An ink composition comprising a colorant and a phase change inkcarrier comprising a compound according to claim
 1. 19. An inkcomposition according to claim 18 wherein the compound of the formula

is present in the ink in an amount of at least about 0.1 percent byweight.
 20. An ink composition according to claim 18 wherein thecompound of the formula

is present in the ink in an amount of at least about 5 percent byweight.
 21. An ink composition according to claim 18 wherein thecompound of the formula

is present in the ink in an amount of no more than about 40 percent byweight.
 22. An ink composition according to claim 18 wherein thecompound of the formula

is present in the ink in an amount of no more than about 20 percent byweight.
 23. A process which comprises (a) incorporating into an ink jetprinting apparatus a phase change ink composition according to claim 18;(b) melting the ink; and (c) causing droplets of the melted ink to beejected in an imagewise pattern onto a substrate.
 24. A processaccording to claim 23 wherein the printing apparatus employs apiezoelectric printing process wherein droplets of the ink are caused tobe ejected in imagewise pattern by oscillations of piezoelectricvibrating elements.
 25. A process according to claim 23 wherein thesubstrate is a final recording sheet and droplets of the melted ink areejected in an imagewise pattern directly onto the final recording sheet.26. A process according to claim 23 wherein the substrate is anintermediate transfer member and droplets of the melted ink are ejectedin an imagewise pattern onto the intermediate transfer member followedby transfer of the imagewise pattern from the intermediate transfermember to a final recording sheet.
 27. A process according to claim 26wherein the intermediate transfer member is heated to a temperatureabove that of the final recording sheet and below that of the melted inkin the printing apparatus.
 28. A process for preparing a compound of theformula

wherein Z is a group of the formula —OR₁, a group of the formula —SR₁,or a group of the formula —NR₁R₂, Y is a group of the formula —OR₃, agroup of the formula —SR₃, or a group of the formula —NR₃R₄, n is aninteger representing the number of repeat —(CH₂)— or —(CH₂CH₂O)— units,wherein, provided that at least one of R₁, R₂, R₃, R₄, and R₆ is ahydrogen atom, provided that at least one of R₁, R₂, R₃, R₄, and R₆ isother than a hydrogen atom, and provided that at least one Z or Y withinthe compound is a group of the formula —NR₁R₂ or a group of the formula—NR₃R₄, R₁, R₂, R₃, R₄, R₆, and R₇ each, independently of the others, is(i) a hydrogen atom, (ii) an alkyl group, (iii) an aryl group, (iv) anarylalkyl group, or (v) an alkylaryl group, and wherein R₇ can also be(vi) an alkoxy group, (vii) an aryloxy group, (viii) an arylalkyloxygroup, (ix) an alkylaryloxy group, (x) a polyalkyleneoxy group, (xi) apolyaryleneoxy group, (xii) a polyarylalkyleneoxy group, (xiii) apolyalkylaryleneoxy group, (xiv) a silyl group, (xv) a siloxane group,(xvi) a polysilylene group, (xvii) a polysiloxane group, or (xviii) agroup of the formula

wherein r is an integer representing a number of repeat —CH₂— groups,wherein s is an integer representing a number of repeating —CH₂— groups,and wherein X is (a) a direct bond, (b) an oxygen atom, (c) a sulfuratom, (d) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogen atom,an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (e) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and wherein R₆ canalso be

which comprises (I) admixing a compound of the formula

with a cyanuric halide at a temperature below about 0° C.; and (II)thereafter adding thereto one or more amines of the formulae R₁R₂NH andR₃R₄NH, wherein R₁, R₂, R₃, and R₄ can be either the same as each otheror different from each other and allowing the reactants to react at atemperature of at least about 60° C., thereby generating a compound ofthe formula


29. A process for preparing a compound of the formula

wherein n is an integer representing the number of repeat —(CH₂)— or—(CH₂CH₂O)— units, wherein, provided that at least one of R₁, R₂, R₃,R₄, and R₅ is a hydrogen atom, provided that at least one of R₁, R₂, R₃,R₄, and R₅ is other than a hydrogen atom, R₁, R₂, R₃, R₄, R₅, and R₇each, independently of the others, is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup, and wherein R₇ can also be (vi) an alkoxy group, (vii) an aryloxygroup, (viii) an arylalkyloxy group, (ix) an alkylaryloxy group, (x) apolyalkyleneoxy group, (xi) a polyaryleneoxy group, (xii) apolyarylalkyleneoxy group, (xiii) a polyalkylaryleneoxy group, (xiv) asilyl group, (xv) a siloxane group, (xvi) a polysilylene group, (xvii) apolysiloxane group, or (xviii) a group of the formula

wherein r is an integer representing a number of repeat —CH₂— groups,wherein s is an integer representing a number of repeating —CH₂— groups,and wherein X is (a) a direct bond, (b) an oxygen atom, (c) a sulfuratom, (d) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogen atom,an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (e) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group which comprises (I)admixing a compound of the formula

with a phosgenating agent and a non-nucleophilic base at a temperaturebelow about 0° C.; and (II) thereafter adding thereto one or more aminesof the formulae R₁R₂NH and R₃R₄NH and R₃R₄NH, wherein R₁, R₂, R₃, and R₄can be either the same as each other or different from each other andallowing the reactants to react at a temperature of at least about 60°C., thereby generating a compound of the formula